Multi-purpose polymers, methods and compositions

ABSTRACT

Disclosed are multi-purpose alkali-swellable and alkali soluble associative polymers, which are the polymerization product of a monomer mixture comprising: (a) at least one acidic vinyl monomer; (b) at least one nonionic vinyl monomer; (c) a first associative monomer having a first hydrophobic end group; (d) a monomer selected from the group consisting of a second associative monomer having a second hydrophobic end, a semihydrophobic monomer and a combination thereof; and, optionally, (e) one or more crosslinking monomers or chain transfer agents. When monomer (d) is an associative monomer, the first and second hydrophobic end groups of monomers (c) and (d) have significantly different hydrophobic and/or steric character from one another. The multi-purpose associative polymers surprisingly provide desirable rheological and aesthetic properties in aqueous media.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.10/338,275 filed on Jan. 8, 2003 (now U.S. Pat. No. 7,288,616) whichclaims priority from U.S. Provisional Application 60/349,399 filed onJan. 18, 2002. The following related, commonly owned application ispending concurrently herewith: U.S. patent application Ser. No.11/482,076 filed on Jul. 6, 2006 which is a divisional application ofU.S. patent application Ser. No. 10/338,510 filed on Jan. 8, 2003 (nowU.S. Pat. No. 7,153,496) which claims priority from U.S. ProvisionalApplication 60/349,608 filed on Jan. 18, 2002.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of anionic polymers, and inparticular, to alkali-swellable and alkali-soluble associative polymers.

BACKGROUND OF THE INVENTION

An associative polymer contains pendant groups capable of formingnon-specific “associations” with other groups in the polymer or othermaterials in the medium in which the polymer is present. Generally thependant group has both hydrophobic and hydrophilic regions and theassociations are generally based on hydrophobic interactions. Hydrogenbonding associations between hydrophilic groups have also been seenunder some pH conditions. According to theory, such associations resultin thickening by the formation of interpolymer networks above a criticalpolymer overlap concentration.

Hydrophobically modified alkali-swellable or alkali soluble emulsionpolymers, conventionally referred to as HASE polymers, are associativepolymers that are typically polymerized as stable emulsions at low pH(pH<4.5) but become water swellable or soluble at near neutral toneutral pH (pH>5.5-7). Typical HASE polymers are vinyl additioncopolymers of pH sensitive or hydrophilic monomers, hydrophobic monomersand an “associative monomer”. The associative monomer has apolymerizable end group, a hydrophilic midsection and a hydrophobic endgroup. An extensive review of HASE polymers is found in Gregory D. Shay,Chapter 25, “Alkali-Swellable and Alkali-Soluble Thickener Technology AReview”, Polymers in Aqueous Media—Performance Through Association,Advances in Chemistry Series 223, J. Edward Glass (ed.), ACS, pp.457-494, Division Polymeric Materials, Washington, D.C. (1989), therelevant disclosures of which are incorporated herein by reference.

Conventional HASE polymers generally contain a single associativemonomer. Conventional HASE polymers may be derived from associativemonomers having a hydrophobic end group which is substantially a singlehydrocarbon moiety or from associative monomers having hydrophobic endgroups which are predominantly mixtures of alkyl groups having molecularformulas differing by about 2 carbon atoms with minor amounts of alkylgroups differing by up to about 6 carbon atoms, for example, alkylgroups derived from some natural fatty materials.

Conventional HASE polymers have been used as rheology modifiers,emulsifiers, stabilizers, solubilizers and pigment grinding additives inindustrial applications. However, HASE polymers have found limitedutility as rheology modifiers in aqueous formulations, because thethickening ability of HASE polymers tends to be relatively low atpractical use levels of about 1% or less. Increasing the amount of HASEpolymer not only is economically undesirable, but highly viscous HASEpolymer solutions can be difficult to handle during manufacturingprocesses on a commercial scale. In addition, increased thickening oftenoccurs at the expense of the optical clarity of the final product, whichis undesirable in certain personal care applications especially for haircare. Consequently, the HASE polymers are conventionally combined withadditional rheology modifying polymers.

Some prior attempts have been made to enhance the thickening ability ofassociative polymers and improve their aqueous thickener performance.For example, U.S. Pat. No. 5,916,967 describes enhancing the thickeningability of associative polymers by mixing the polymer with two or moresurfactants. Similarly, surfactant-thickener interactions are disclosedby C. E. Jones in “A Study of the Interaction ofHydrophobically-Modified Polyols with Surfactants”, Proceedings of the4th World Surfactants Congress, CESIO, Barcelona, 2, 439-450 (1996) andby P. Reeve in “Tailoring the Properties of Polymeric Rheology Modifiersto the Characteristics and Requirements of Personal Care Formulations”,Proceedings of International Federation of Society of Cosmetic Chemists,IFSCC, Budapest, 337-346 (April 1997).

An approach for improving the thickening properties of aqueous solutionsusing macromonomer-derived associative polymers employing surfactants asco-thickeners is disclosed in U.S. Pat. No. 5,292,843. European PatentApplication No. 1,038,892A2 describes adding a mixture of at least onemultiphobe and at least one monophobe compound (as an additive)particularly to improve the viscosity stability of an aqueous systemcontaining at least one associative thickener. A method of suppressingthe viscosity of HASE polymers in aqueous compositions by complexationof the hydrophobic moieties of the polymer with cyclodextrin compounds(capping agent additive) is disclosed in U.S. Pat. No. 5,137,571 andU.S. Pat. No. 6,063,857.

There is an ongoing, unresolved need and desire for an associativepolymer having improved rheological and aesthetic properties in anaqueous media. The multi-purpose alkali-swellable associative polymers(ASAP) of the present invention surprisingly provide such desirablerheological and aesthetic properties in aqueous media.

SUMMARY OF THE INVENTION

The present invention discloses multi-purpose, alkali-swellable andalkali-soluble associative polymers, referred to herein as ASAP.

The ASAP of the present invention are the polymerization product of amonomer mixture comprising (a) at least one acidic vinyl monomer; (b) atleast one nonionic vinyl monomer; (c) a first associative monomer havinga first hydrophobic end group; (d) at least one monomer selected fromthe group consisting of a second associative monomer having a secondhydrophobic end, a semihydrophobic monomer and a combination thereof;and, optionally, (e) one or more crosslinking monomers or chain transferagents. When a second associative monomer (d) is included in thepolymerization, the first and second hydrophobic end groups of theassociative monomers (c) and (d) have significantly differenthydrophobic and/or steric character from one another.

The ASAP of the present invention can provide products havingrheological properties ranging from pourable liquids to non-pourablegels, as well as non-runny, yet flowable, compositions, withoutrequiring additional or auxiliary rheology modifiers. The inventivepolymers can also suspend abrasives, pigments, particulates, waterinsoluble materials, such as encapsulated oil beads, liposomes,capsules, gaseous bubbles, and the like.

Advantageously, the associative polymers of this invention can beemployed, without being limited thereto, in personal care products,health care products, household care products, non-household,institutional and industrial care products, and the like and inindustrial chemical processes and applications as, for example, rheologymodifiers, film formers, thickeners, emulsifiers, stabilizers,solubilizers, suspending agents, and pigment grinding additives. Thealkali-swellable, associative polymers are particularly useful asthickeners in textile treatment compositions for finishing, coating andprinting applications, and the like. The alkali-soluble, associativepolymers are particularly useful for thin viscosity, sprayable and foamcompositions.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, the term ASAP includes the singular or plural form andrefers to acidic/anionic water-swellable or water-soluble, associativepolymers, and salts thereof, which contain two or more non-identicalhydrophobically modified polyoxyethylene groups, or which contain atleast one hydrophobically modified polyoxyalkylene group and at leastone non-hydrophobically modified polyoxyalkylene group. The ASAP mayalso optionally contain other monomer units, such as crosslinkingmonomer units, or chain transfer agent units.

It has been surprisingly discovered that the ASAPs are suitable for usein aqueous personal care, health care, household care, and institutionaland industrial care (“I&I”) products and provide or attenuate rheologymodification while retaining and enhancing the desired performance andaesthetic properties of the polymer containing products.

The term “personal care products” as used herein includes, without beinglimited thereto, cosmetics, toiletries, cosmeceuticals, beauty aids,personal hygiene and cleansing products applied to the body, includingthe skin, hair, scalp, and nails of humans and animals. The term “healthcare products” as used herein includes, without being limited thereto,pharmaceuticals, pharmacosmetics, oral care (mouth and teeth) products,such as oral suspensions, mouthwashes, toothpastes, and the like, andover-the-counter products and appliances, such as patches, plasters andthe like, externally applied to the body, including the skin, scalp,nails and mucous membranes of humans and animals, for ameliorating ahealth-related or medical condition, for generally maintaining hygieneor well-being, and the like. The term “household care products” as usedherein includes, without being limited thereto, products employed in adomestic household for surface cleaning or maintaining sanitaryconditions, such as in the kitchen and bathroom, and laundry productsfor fabric care and cleaning, and the like. The term “institutional andindustrial care” and “I&I” as used herein includes, without beinglimited thereto, products employed for surface cleaning or maintainingsanitary conditions in institutional and industrial environments,textile treatments, and the like.

As used herein and in the appended claims the term “rheologicalproperties” and grammatical variations thereof, includes, withoutlimitation such properties as Brookfield viscosity, increase or decreasein viscosity in response to shear stress, flow characteristics, gelproperties such as stiffness, resilience, flowability, and the like,foam properties such as foam stability, foam density, ability to hold apeak, and the like, and aerosol properties such as ability to formaerosol droplets when dispensed from propellant-based or mechanicalpump-type aerosol dispensers. The term “aesthetic property” andgrammatical variations thereof as applied to compositions refers tovisual and tactile psychosensory product properties, such as color,clarity, smoothness, tack, lubricity, texture, and the like.

The alkali-swellable, associative polymer embodiments of this inventionare particularly useful as rheology modifiers in aqueous textiletreatment compositions. The term “textile” as used herein includesnatural and synthetic fibers in woven or non-woven form, natural andsynthetic leathers, and the like. Surprisingly, the inventivealkali-swellable ASAP have been found to be more efficient thickenersthan conventional HASE polymer making them suitable for use in textileapplications, such as printing, coating, saturation, dyeing, and liketextile treatment operations.

The alkali-soluble, associative polymer embodiments of this inventionare particularly useful as foam enhancers and as film formers inaqueous, and low VOC (volatile organic compounds) or high VOCpressurized or non-pressurized aerosols.

The term “aqueous” as applied to formulations or media means that wateris present in an amount sufficient to at least swell or dissolve theASAP in the composition into which it is included.

The alkali-swellable and alkali-soluble associative polymers (ASAP) ofthe present invention are multi-purpose polymers, which are preferablyprepared by polymerizing a monomer mixture containing: (a) at least oneacidic vinyl monomer or salt thereof; (b) at least one nonionic vinylmonomer; (c) a first associative monomer having a first hydrophobic endgroup; (d) at least one monomer selected from the group consisting of asecond associative monomer having a second hydrophobic end group, asemihydrophobic monomer, and a combination thereof; and, optionally (e)one or more crosslinking monomer or chain transfer agent. When a secondassociative monomer (d) is included in the polymerization mixture, thefirst and second hydrophobic end groups of the associative monomers (c)and (d) are each independently selected from the same or differenthydrocarbon classes, with the proviso that when the first and secondhydrophobic end groups are chosen from the same hydrocarbon class, themolecular formulas of the two hydrophobic end groups differ from oneanother by at least about 8 carbon atoms. When the polymer comprises twoor more associative monomers, the weight ratio of at least two of theassociative monomers to one another in the mixture preferably is in therange of about 1:1 to 100:1, more preferably 1:1 to about 20:1, mostpreferably 1:1 to about 10:1.

In one preferred embodiment, the multi-purpose ASAP is thepolymerization product of a monomer mixture comprising, on a totalmonomer mixture weight basis:

(a) about 10 to about 75 weight percent of at least one acidic vinylmonomer or a salt thereof;

(b) about 10 to about 90 weight percent of at least one nonionic vinylmonomer;

(c) about 0.1 to about 25 weight percent of a first associative monomerhaving a first hydrophobic end group;

(d) about 0.1 to about 25 weight percent of at least one monomerselected from the group consisting of a second associative monomerhaving a second hydrophobic end group, a semihydrophobic monomer and acombination thereof; and, optionally,

(e) about 0.01 to about 20 weight percent of one or more monomersselected from the group consisting of a crosslinking monomer, a chaintransfer agent, and a combination thereof.

A particularly preferred alkali-swellable associative polymer embodimentof the present invention is the product of polymerization of a monomermixture comprising, on a total monomer mixture weight basis: (a) about30 to about 75 weight percent of at least one acidic vinyl monomer or asalt thereof; (b) at least about 25 weight percent, but not more than 60weight percent of at least one nonionic vinyl monomer; (c) about 0.5 toabout 20 weight percent of a first associative monomer having a firsthydrophobic end group; (d) about 0.5 to about 20 weight percent of atleast one monomer selected from the group consisting of a secondassociative monomer having a second hydrophobic end group, asemihydrophobic monomer, and a combination thereof; and, optionally, (e)up to about 20 weight percent of a crosslinking monomer. When monomer(d) is a second associative monomer, the first and second hydrophobicend groups of associative monomers (c) and (d) are each independentlyselected from the same or different hydrocarbon classes. When the firstand second hydrophobic end groups are selected from the same hydrocarbonclass, the molecular formulas of the hydrophobic end groups differ by atleast about 8 carbon atoms. The associative polymers of this preferredembodiment are alkali-swellable and provide excellent rheology modifyingcharacteristics, providing relatively high viscosity to alkaline aqueoussystems in which the polymer is present. Examples of these preferredalkali-swellable polymers are provided in Tables 2A-2C, below.

Another preferred embodiment of the present invention is analkali-soluble, relatively low viscosity associative polymer. Thealkali-soluble associative polymer of this preferred embodiment is theproduct of polymerization of a monomer mixture comprising, on a totalmonomer mixture weight basis: (a) about 10 to about 30 weight percent ofat least one acidic vinyl monomer or a salt thereof; (b) more than 60weight percent of at least one nonionic vinyl monomer; (c) about 0.5 toabout 5 weight percent of at least one associative monomer having ahydrophobic end group; (d) about 0.5 to about 5 weight percent of atleast one semihydrophobic monomer having a polymerizable, unsaturatedend group and a polyoxyalkylene group covalently bonded thereto; and (e)about 0.5 to about 5 weight percent of a chain transfer agent. Thealkali-soluble associative polymers of this preferred embodiment providegood film-forming and humidity resistance properties, making themsuitable for compositions, such as pumpable or sprayable hydro-alcoholiccompositions, where a thin viscosity is desirable. Examples of thesepreferred alkali-soluble associative polymers are provided in Table 2D,below.

Preferably, the hydrophobic end groups of the associative monomersutilized in the polymers of the present invention are selected from thegroup consisting of a C₈-C₄₀ linear alkyl, a C₈-C₄₀ branched alkyl, aC₈-C₄₀ carbocyclic alkyl, an aryl-substituted C₂-C₄₀ alkyl, a C₂-C₄₀alkyl-substituted phenyl, and a C₈-C₈₀ complex ester.

The first and second hydrophobic end groups of the associative monomercomponents can be selected from the same or different hydrocarbonclasses. However, when a second associative monomer is present, and boththe first and second associative monomers have hydrophobic end groupsbelonging to the same hydrocarbon class (e.g., both hydrophobic endgroups are C₈-C₄₀ linear alkyl groups) then, the molecular formulas ofthe hydrophobic end groups are selected to differ from each otherpreferably by at least about 12 carbon atoms, more preferably by atleast about 10 carbon atoms, and most preferably by at least about 8carbon atoms.

In a particularly preferred embodiment, at least one associative monomerhas a hydrophobic end group which is a C₁₂-C₄₀ linear alkyl group.

When more than two associative monomers are utilized to prepare the ASAPof the present invention, preferably at least two of the associativemonomers have hydrophobic end groups selected from different hydrocarbonclasses. When more than two associative monomers are utilized to preparethe ASAP of the present invention, and all of the utilized associativemonomers have hydrophobic end groups selected from the same hydrocarbonclass, the molecular formula of the hydrophobic end group having thelargest number of carbon atoms preferably has at least about 12 morecarbon atoms, more preferably at least about 10 more carbon atoms, andmost preferably at least about 8 more carbon atoms, than the molecularformula of the hydrophobic end group having the least number of carbonatoms.

However, when the polymerization mixture comprises a combination of asecond associative monomer and a semihydrophobic monomer, there is nolimitation as to the molecular formulas of the first and secondhydrophobic end groups of the associative monomers. When thepolymerization mixture includes a semihydrophobic monomer and two ormore associative monomers, the first and second associative monomers cancomprise any combination of first and second hydrophobic end groups,without limitation as to hydrocarbon class or number of carbon atoms inmolecular formulas of their respective hydrophobic end groups.

The terms “first” and “second” as used herein in relation to associativemonomers and their respective hydrophobic end groups means that two ormore different associative monomers are employed, and are not intendedto imply any temporal relationship in the addition of the monomers tothe reaction mixture, nor are the terms intended to connote anyfunctional difference between the monomers or hydrophobic end groups.The term “(meth)acrylate” includes, alternatively, acrylate ormethacrylate, and the term “(meth)acrylamide” includes, alternatively,acrylamide or methacrylamide.

As used herein the term “alkyl” means a substituted or unsubstitutedaliphatic hydrocarbon moiety; the term “carbocyclic alkyl” means analkyl group comprising one or more carbocyclic rings of from 3 to about12 carbon atoms in size; and the term “aryl” means a substituted orunsubstituted phenyl or naphthyl moiety. Modifiers of the form“C_(x)-C_(y)” designate that the alkyl or carbocyclic alkyl groups havemolecular formulas containing a total of x to y carbon atoms, where xand y are specified integers. The terms “halogen-substituted”,“hydroxy-substituted”, “carboxy-substituted”,“polyoxyalkylene-substituted”, alkyl-substituted”, and“aryl-substituted” as used herein in reference to alkyl or aryl groups,and the like, mean that at least one hydrogen atom on an alkyl, aryl, orlike group has been replaced by at least one halogen atom, hydroxylgroup, carboxyl group, polyoxyalkylene group, alkyl group, or arylgroup, respectively.

Suitable monomers useful in the preparation of the multi purposeassociative polymers of the present invention are as described below.

Acidic Vinyl Monomer

Acidic vinyl monomers suitable for use in the present invention areacidic, polymerizable, ethylenically unsaturated monomers preferablycontaining at least one carboxylic acid, sulfonic acid group, or aphosphonic acid group to provide an acidic or anionic functional site.These acid groups can be derived from monoacids or diacids, anhydridesof dicarboxylic acids, monoesters of diacids, and salts thereof.

Suitable acidic vinyl carboxylic acid-containing monomers include, butare not limited to: acrylic acid, methacrylic acid, itaconic acid,citraconic acid, maleic acid, fumaric acid, crotonic acid, aconiticacid, and the like, and C₁-C₁₈ alkyl-monoesters of maleic, fumaric,itaconic, or aconitic acid, such as methyl hydrogen maleate,monoisopropyl maleate, butyl hydrogen fumarate, and the like. Anhydridesof dicarboxylic acids, such as maleic anhydride, itaconic anhydride,citraconic anhydride, and the like can also be utilized as acidic vinylmonomers. Such anhydrides generally hydrolyze to the correspondingdiacids upon prolonged exposure to water, or at elevated pH.

Suitable sulfonic acid group-containing monomers include, but are notlimited to: vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS),allyloxybenzene sulfonic acid, and the like. Particularly preferred arethe sodium salt of styrene sulfonic acid (SSSA) and AMPS.

Non-limiting examples of suitable phosphonic acid group-containingmonomers include vinyl phosphonic acid, allyl phosphonic acid,3-acrylamidopropyl phosphonic acid, and the like.

Suitable salts include, without limitation thereto, alkali metal salts,such as sodium, potassium and lithium salts; alkaline earth metal salts,such as calcium and magnesium salts; ammonium salts; andalkyl-substituted ammonium salts, such as salts of2-amino-2-methyl-1-propanol (AMP), ethanolamine, diethanolamine,triethanolamine, triethylamine, and the like.

The foregoing monomers or salts thereof can be used as the acidic vinylmonomer component of the inventive ASAP, individually, or in mixtures oftwo or more. Acrylic acid, methacrylic acid, the sodium salt of styrenesulfonic acid (SSSA), AMPS as well as fumaric acid, maleic acid,itaconic acid, and monoesters or monoamides thereof, are preferred.Particularly preferred acidic vinyl monomers are acrylic and methacrylicacid, SSSA, and AMPS.

The acidic vinyl monomer preferably comprises about 10 to about 75weight percent of the total monomer mixture, more preferably about 25 toabout 65 weight percent, and most preferably about 30 to about 60 weightpercent, on a total monomer mixture weight basis.

Nonionic Monomer

Nonionic vinyl monomers suitable for use in the present invention arecopolymerizable, nonionic, ethylenically unsaturated monomers, which arewell known in the art. Preferred nonionic vinyl monomers are compoundshaving either of the following formulas (I) or (II):CH₂═C(X)Z,  (I)CH₂═CH—OC(O)R;  (II)wherein, in each of formulas (I) and (II), X is H or methyl; and Z is—C(O)OR¹, —C(O)NH₂, —C(O)NHR¹, —C(O)N(R¹)₂, —C₆H₄R¹, —C₆H₄OR¹, —C₆H₄Cl,—CN, —NHC(O)CH₃, —NHC(O)H, N-(2-pyrrolidonyl), N-caprolactamyl,—C(O)NHC(CH₃)₃, —C(O)NHCH₂CH₂—N-ethyleneurea, —SiR₃,—C(O)O(CH₂)_(x)SiR₃, —C(O)NH(CH₂)_(x)SiR₃, or —(CH₂)_(x)SiR₃; x is aninteger in the range of 1 to about 6; each R is independently C₁-C₁₈alkyl; each R¹ is independently C₁-C₃₀ alkyl, hydroxy-substituted C₂-C₃₀alkyl, or halogen-substituted C₁-C₃₀ alkyl.

Non-limiting examples of suitable water-insoluble, nonionic vinylmonomers include C₁-C₃₀ alkyl(meth)acrylates; C₁-C₃₀ alkyl(meth)acrylamides; styrene; substituted styrenes, such as vinyl toluene(e.g., 2-methyl styrene), butyl styrene, isopropyl styrene, p-chlorostyrene, and the like; vinyl esters, such as vinyl acetate, vinylbutyrate, vinyl caprolate, vinyl pivalate, vinyl neodecanoate, and thelike; unsaturated nitriles, such as methacrylonitrile, acrylonitrile,and the like; and unsaturated silanes, such as trimethylvinylsilane,dimethylethylvinylsilane, allyldimethylphenylsilane,allytrimethylsilane, 3-acrylamidopropyltrimethylsilane,3-trimethylsilylpropyl methacrylate, and the like.

Non-limiting examples of suitable water-soluble nonionic vinyl monomersare C₂-C₆ hydroxyalkyl(meth)acrylates; glycerol mono(meth)acrylate;tris(hydroxymethyl)ethane mono(meth)acrylate; pentaerythritolmono(meth)acrylate; N-hydroxymethyl(meth)acrylamide;2-hydroxyethyl(meth)acrylamide; 3-hydroxypropyl(meth)acrylamide;(meth)acrylamide; N-vinyl caprolactam; N-vinyl pyrrolidone;methacrylamidoethyl-N-ethyleneurea (e.g.,CH₂═C(CH₃)C(O)NHCH₂CH₂—N-ethyleneurea), C₁-C₄ alkoxy-substituted(meth)acrylates and (meth)acrylamides, such asmethoxyethyl(meth)acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate, andthe like; and combinations thereof.

Particularly preferred nonionic vinyl monomers include C₁-C₁₈ alkylesters of acrylic acid and of methacrylic acid,methacrylamidoethyl-N-ethylene urea, and combinations thereof.

The nonionic vinyl monomer preferably comprises about 10 to about 90weight percent of the total monomer mixture, more preferably about 25 toabout 75 weight percent, and most preferably about 30 to about 60 weightpercent, on a total monomer mixture weight basis.

Associative Monomer

Associative monomers suitable for the production of the inventive ASAPare compounds preferably having an ethylenically unsaturated end groupportion (i) for addition polymerization with the other monomers of thesystem; a polyoxyalkylene midsection portion (ii) for impartingselective hydrophilic properties to the product polymer and ahydrophobic end group portion (iii) for providing selective hydrophobicproperties to the polymer.

The portion (i) supplying the ethylenically unsaturated end grouppreferably is derived from an α,β-ethylenically unsaturated mono ordi-carboxylic acid or the anhydride thereof, more preferably a C₃ or C₄mono- or di-carboxylic acid or the anhydride thereof. Alternatively,portion (i) of the associative monomer can be derived from an allylether or vinyl ether; a nonionic vinyl-substituted urethane monomer,such as disclosed in U.S. Reissue Pat. No. 33,156 or U.S. Pat. No.5,294,692; or a vinyl-substituted urea reaction product, such asdisclosed in U.S. Pat. No. 5,011,978; the relevant disclosures of eachare incorporated herein by reference.

The midsection portion (ii) is preferably a polyoxyalkylene segment ofabout 5 to about 250, more preferably about 10 to about 120, and mostpreferably about 15 to about 60 repeating C₂-C₇ alkylene oxide units.Preferred midsection portions (ii) include polyoxyethylene,polyoxypropylene, and polyoxybutylene segments comprising about 5 toabout 150, more preferably about 10 to about 100, and most preferablyabout 15 to about 60 ethylene, propylene or butylene oxide units, andrandom or non-random sequences of ethylene oxide, propylene oxide and orbutylene oxide units.

The hydrophobic end group portion (iii) of the associative monomers ispreferably a hydrocarbon moiety belonging to one of the followinghydrocarbon classes: a C₈-C₄₀ linear alkyl, an aryl-substituted C₂-C₄₀alkyl, a C₂-C₄₀ alkyl-substituted phenyl, a C₈-C₄₀ branched alkyl, aC₈-C₄₀ carbocyclic alkyl; and a C₈-C₈₀ complex ester.

As used herein and in the appended claims, the term “complex ester”means a di-, tri-, or poly-ester of a polyol such as a sugar, having atleast one hydroxyl group capable of being alkylated with a C₂-C₇alkylene oxide. The term “complex ester” includes, in particular, thecomplex hydrophobes described by Jenkins et al. in U.S. Pat. No.5,639,841, the relevant disclosure of which is incorporated herein byreference.

Non-limiting examples of suitable hydrophobic end group portions (iii)of the associative monomers are linear or branched alkyl groups havingabout 8 to about 40 carbon atoms, such as capryl (C₈), iso-octyl(branched C₈), decyl (C₁₀), lauryl (C₁₂), myristyl (C₁₄), cetyl (C₁₆),cetearyl (C₁₆-C₁₈), stearyl (C₁₈), isostearyl (branched C₁₈), arachidyl(C₂₀), behenyl (C₂₂), lignoceryl (C₂₄), cerotyl (C₂₆), montanyl (C₂₈),melissyl (C₃₀), lacceryl (C₃₂), and the like.

Examples of linear and branched alkyl groups having about 8 to about 40carbon atoms that are derived from a natural source include, withoutbeing limited thereto, alkyl groups derived from hydrogenated peanutoil, soybean oil and canola oil (all predominately C₁₈), hydrogenatedtallow oil (C₁₆-C₁₈), and the like; and hydrogenated C₁₀-C₃₀ terpenols,such as hydrogenated geraniol (branched C₁₀), hydrogenated farnesol(branched C₁₅), hydrogenated phytol (branched C₂₀), and the like.

Non-limiting examples of suitable C₂-C₄₀ alkyl-substituted phenyl groupsinclude octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl,hexadecylphenyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl, andthe like.

Suitable C₈-C₄₀ carbocylic alkyl groups include, without being limitedthereto, groups derived from sterols from animal sources, such ascholesterol, lanosterol, 7-dehydrocholesterol, and the like; fromvegetable sources, such as phytosterol, stigmasterol, campesterol, andthe like; and from yeast sources, such as ergosterol, mycosterol, andthe like. Other carbocyclic alkyl hydrophobic end groups useful in thepresent invention include, without being limited thereto, cyclooctyl,cyclododecyl, adamantyl, decahydronaphthyl, and groups derived fromnatural carbocyclic materials, such as pinene, hydrogenated retinol,camphor, isobornyl alcohol, and the like.

Exemplary aryl-substituted C₂-C₄₀ alkyl groups include, withoutlimitation thereto, styryl (e.g., 2-phenylethyl), distyryl (e.g.,2,4-diphenylbutyl), tristyryl (e.g., 2,4,6-triphenylhexyl),4-phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenolyl, and the like.

Non-limiting examples of suitable C₈-C₈₀ complex esters includehydrogenated castor oil (predominately the triglyceride of12-hydroxystearic acid); 1,2-diacyl glycerols, such as 1,2-distearylglycerol, 1,2-dipalmityl glycerol, 1,2-dimyristyl glycerol, and thelike; di-, tri-, or poly-esters of sugars, such as 3,4,6-tristearylglucose, 2,3-dilauryl fructose, and the like; and sorbitan esters, suchas those disclosed in U.S. Pat. No. 4,600,761 to Ruffner et al., thepertinent disclosures of which are incorporated herein by reference.

Useful associative monomers can be prepared by any method known in theart. See, for example, U.S. Pat. No. 4,421,902 to Chang et al.; U.S.Pat. No. 4,384,096 to Sonnabend; U.S. Pat. No. 4,514,552 to Shay et al.;U.S. Pat. No. 4,600,761 to Ruffner et al.; U.S. Pat. No. 4,616,074 toRuffner; U.S. Pat. No. 5,294,692 to Barron et al.; U.S. Pat. No.5,292,843 to Jenkins et al.; U.S. Pat. No. 5,770,760 to Robinson; andU.S. Pat. No. 5,412,142 to Wilkerson, III et al.; the pertinentdisclosures of which are incorporated herein by reference.

Examples of preferred associative monomers include those having formula(III).

whereineach R² is independently H, methyl, —C(O)OH, or —C(O)OR³; R³ is C₁-C₃₀alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—, —C(O)NH—,—Ar—(CE₂)_(z)—NHC(O)O—, —Ar—(CE₂)_(z)—NHC(O)NH—, or —CH₂CH₂NHC(O)—; Aris a divalent aryl; E is H or methyl; z is 0 or 1; k is an integer inthe range of 0 to about 30, and m is 0 or 1, with the proviso that whenk is 0, m is 0, and when k is in the range of 1 to about 30, m is 1;(R⁴—O)_(n) is a polyoxyalkylene, which is a homopolymer, a randomcopolymer, or a block copolymer of C₂-C₄ oxyalkylene units, wherein R⁴is C₂H₄, C₃H₆, or C₄H₈, and n is an integer in the range of about 5 toabout 250, preferably about 5 to about 100, more preferably about 10 toabout 80, and most preferably about 15 to about 60; Y is —R⁴O—, —R⁴NH—,—C(O)—, —C(O)NH—, —R⁴NHC(O)NH—, or —C(O)NHC(O)—; R⁵ is a substituted orunsubstituted alkyl selected from the group consisting of a C₈-C₄₀linear alkyl, a C₈-C₄₀ branched alkyl, a C₈-C₄₀ carbocyclic alkyl, aC₂-C₄₀ alkyl-substituted phenyl, an aryl-substituted C₂-C₄₀ alkyl, and aC₈-C₈₀ complex ester; wherein the R⁵ alkyl group optionally comprisesone or more substituents selected from the group consisting of ahydroxyl group, an alkoxyl group, and a halogen group.

Particularly preferred associative monomers of formula (III) includecetyl polyethoxylated methacrylate (CEM), cetearyl polyethoxylatedmethacrylate (CSEM), stearyl polyethoxylated (meth)acrylate, arachidylpolyethoxylated (meth)acrylate, behenyl polyethoxylated methacrylate(BEM), cerotyl polyethoxylated (meth)acrylate, montanyl polyethoxylated(meth)acrylate, melissyl polyethoxylated (meth)acrylate, laccerylpolyethoxylated (meth)acrylate, tristyrylphenol polyethoxylatedmethacrylate (TEM), hydrogenated castor oil polyethoxylated methacrylate(HCOEM), canola polyethoxylated (meth)acrylate, and cholesterolpolyethoxylated methacrylate (CHEM), where the polyethoxylated portionof the monomer comprises about 5 to about 100, preferably about 10 toabout 80, and more preferably about 15 to about 60 ethylene oxiderepeating units.

Preferably, the associative monomer components in the monomer mixtureindependently comprise, on a total monomer mixture weight basis, about0.1 to about 25 weight percent of the monomer mixture, more preferablyabout 0.25 to about 20 weight percent, most preferably about 0.5 toabout 15 weight percent.

Semihydrophobic Monomer

It was surprisingly found that a semihydrophobic monomer (SH monomer)can moderate the associative properties of polymers containing them,thus producing aqueous gels with highly desirable texture andrheological properties. Not wishing to be bound by theory, it is thoughtthat the polyoxyalkylene group of the SH monomer interrupts or shieldsagainst non-specific associations between the hydrophobic groups of theassociative monomers in the polymer, or external components and thusattenuates the associative properties of the polymers. Such SH monomerscan tailor the thickening efficiency of the resulting polymers tocustomize the rheological properties of the polymer as desired for aselected application. Most surprisingly, alkali-swellable polymerscontaining the SH monomers were found to impart desirable rheologicaland aesthetic properties to aqueous gels, generally providing softer,smoother and more spreadable gels at all polymer concentrations than didalkali-swellable associative polymers containing no SH monomer andprovided a Brookfield viscosity that remained substantially unchangedover a period of 24 hours.

Surprisingly, incorporation of a SH monomer into an alkali-swellableassociative polymer can reduce gel viscosity at low shear stress,minimize or eliminate viscosity reduction as shear stress is increasedand minimize or decrease shear thinning behavior of the gels. Forexample, Polymer CP-5, described in Example 1 below, having 3% BEM25associative monomer, when measured by a complex viscosity technique atan active polymer weight concentration of about 1.2%, had a viscosity of178 Pa·s (178,000 cP) at a shear stress of 1 Pa; and increasing theshear stress to 5 Pa led to a reduction in complex viscosity to 43.6Pa·s. Adding a SH monomer to the polymer, e.g. as in Polymer AG, Example1, which has 3% BEM25 and 5% of the SH monomer R307, had two effects.First, the complex viscosity measured at an active polymer weightconcentration of about 1.2% at 1 Pa shear stress was reduced to 106Pa·s. Second, upon increasing the shear stress to 5 Pa, the complexviscosity measurement remained almost unchanged (105.5 Pa·s). Similarly,when 15% of SH monomer was incorporated (e.g., as in Polymer AI, Example1), the complex viscosity measured at an active polymer weightconcentration of about 1.2% at 1 Pa shear stress was 46.5 Pa·s, whereasat 5 Pa shear stress the complex viscosity measured was 36 Pa·s.

As used herein and in the appended claims, the terms “semihydrophobicmonomer” and “SH monomers” refer to compounds having two portions: (i)an ethylenically unsaturated end group portion for additionpolymerization with the other monomers of the reaction mixture, and (ii)a polyoxyalkylene portion for attenuating the associations between thehydrophobic groups of the polymer or hydrophobic groups from othermaterials in a composition containing the polymer. A semihydrophobicmonomer is similar to an associative monomer, but has a substantiallynon-hydrophobic end group portion.

The unsaturated end group portion (i) supplying the vinyl or otherethylenically unsaturated end group for addition polymerization ispreferably derived from an α,β-ethylenically unsaturated mono ordi-carboxylic acid or the anhydride thereof, preferably a C₃ or C₄ mono-or di-carboxylic acid, or the anhydride thereof. Alternatively, the endgroup portion (i) can be derived from an allyl ether, a vinyl ether or anonionic urethane monomer.

The polymerizable unsaturated end group portion (i) can also be derivedfrom a C₈-C₃₀ unsaturated fatty acid group containing at least one freecarboxy-functional group. This C₈-C₃₀ group is part of the unsaturatedend group portion (i) and is different from the hydrophobic groupspendant to the associative monomers, which are specifically separatedfrom the unsaturated end group of the associative monomer by ahydrophilic “spacer” portion.

The polyoxyalkylene portion (ii) specifically comprises a long-chainpolyoxyalkylene segment, which is substantially similar to thehydrophilic portion of the associative monomers. Preferredpolyoxyalkylene portions (ii) include polyoxyethylene, polyoxypropylene,and polyoxybutylene units comprising about 2 to about 250, andpreferably about 10 to about 100 ethylene oxide, propylene oxide, orbutylene oxide units, or random or non-random sequences of ethyleneoxide, propylene oxide, and/or butylene oxide units.

Preferred SH monomers include those having either of the followingformulas (IV) or (V):

wherein, in each of formulas (IV) and (V),each R⁶ is independently H, C₁-C₃₀ alkyl, —C(O)OH, or —C(O)OR⁷; R⁷ isC₁-C₃₀ alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—,—C(O)NH—, —Ar—(CE₂)_(z)—NHC(O)O—, —Ar—(CE₂)_(z)—NHC(O)NH—, or—CH₂CH₂NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; pis an integer in the range of 0 to about 30, and r is 0 or 1, with theproviso that when p is 0, r is 0, and when p is in the range of 1 toabout 30, r is 1; (R⁸—O)_(v) is a polyoxyalkylene, which is ahomopolymer, a random copolymer, or a block copolymer of C₂-C₄oxyalkylene units, wherein R⁸ is C₂H₄, C₃H₆, or a mixture thereof, and vis an integer in the range of about 5 to about 250, preferably about 5to about 100, more preferably about 10 to about 80, and most preferablyabout 15 to about 60; R⁹ is H or C₁-C₄ alkyl; and D is a C₈-C₃₀unsaturated alkyl or a carboxy-substituted C₈-C₃₀ unsaturated alkyl.

Particularly preferred semihydrophobic monomers include monomers havingthe following chemical formulas:CH₂═CH—O—(CH₂)_(a)—O—(C₃H₆O)_(b)—(C₂H₄O)_(c)—H orCH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(e)—H;wherein a, preferably, is 2, 3, or 4; b, preferably, is an integer inthe range of 1 to about 10, more preferably about 2 to about 8, mostpreferably about 3 to about 7; c, preferably, is an integer in the rangeof about 5 to about 50, more preferably about 8 to about 40, mostpreferably about 10 to about 30; d, preferably, is an integer in therange of 1 to about 10, more preferably about 2 to about 8, mostpreferably about 3 to about 7; and e, preferably, is an integer in therange of about 5 to about 50, more preferably about 8 to about 40.

Examples of preferred SH monomers include polymerizable emulsifierscommercially available under the trade names EMULSOGEN® R109, R208,R307, RAL109, RAL208, and RAL307 sold by Clariant Corporation;BX-AA-E5P5 sold by Bimax, Inc.; and MAXEMUL® 5010 and 5011 sold byUniqema; and combinations thereof. Particularly preferred SH monomersinclude EMULSOGEN® R109, R208, and R307, BX-AA-E5P5, MAXEMUL® 5010 and5011, and combinations thereof.

According to the manufacturers: EMULSOGEN® R109 is a randomlyethoxylated/propoxylated 1,4-butanediol vinyl ether having the empiricalformula CH₂—CH—O(CH₂)₄O(C₃H₆O)₄(C₂H₄O)₁₀H; EMULSOGEN® R208 is a randomlyethoxylated/propoxylated 1,4-butanediol vinyl ether having the empiricalformula CH₂═CH—O(CH₂)₄O(C₃H₆O)₄(C₂H₄O)₂₀H; EMULSOGEN® R307 is a randomlyethoxylated/propoxylated 1,4-butanediol vinyl ether having the empiricalformula CH₂═CH—O(CH₂)₄O(C₃H₆O)₄(C₂H₄O)₃₀H; EMULSOGEN® RAL109 is arandomly ethoxylated/propoxylated allyl ether having the empiricalformula CH₂═CHCH₂O(C₃H₆O)₄(C₂H₄O)₁₀H; EMULSOGEN® RAL208 is a randomlyethoxylated/propoxylated allyl ether having the empirical formulaCH₂═CHCH₂O(C₃H₆O)₄(C₂H₄O)₂₀H; EMULSOGEN® RAL307 is a randomlyethoxylated/propoxylated allyl ether having the empirical formulaCH₂═CHCH₂O(C₃H₆O)₄(C₂H₄O)₃₀H; MAXEMUL® 5010 is a carboxy-functionalC₁₂-C₁₅ alkenyl hydrophobe, ethoxylated with about 24 ethylene oxideunits; MAXEMUL® 5011 is a carboxy-functional C₁₂-C₁₅ alkenyl hydrophobe,ethoxylated with about 34 ethylene oxide units; and BX-AA-E5P5 is arandomly ethoxylated/propoxylated allyl ether having the empiricalformula CH₂═CHCH₂O(C₃H₆O)₅(C₂H₄O)₅H.

The amount of semihydrophobic monomers utilized in the preparation ofthe polymers of the present invention can vary widely and depends, amongother things, on the final rheological and aesthetic properties desiredin the polymer. When utilized, the monomer reaction mixture preferablycontains one or more semihydrophobic monomers in amounts in the range ofabout 0.1 to about 25 weight percent based on the total monomer mixtureweight, more preferably about 0.5 to about 20 weight percent, mostpreferably about 1 to about 15 weight percent.

Crosslinking Monomer

The ASAP can optionally be prepared from a monomer mixture comprisingone or more crosslinking monomer for introducing branching andcontrolling molecular weight. Suitable polyunsaturated crosslinkers arewell known in the art. Mono-unsaturated compounds carrying a reactivegroup that is capable of causing a formed copolymer to be crosslinkedbefore, during, or after polymerization has taken place can also beutilized. Other useful crosslinking monomers include polyfunctionalmonomers containing multiple reactive groups, such as epoxide groups,isocyanate groups, and hydrolyzable silane groups. Variouspolyunsaturated compounds can be utilized to generate either a partiallyor substantially cross-linked three dimensional network.

Examples of suitable polyunsaturated crosslinking monomer componentsinclude, without being limited thereto, polyunsaturated aromaticmonomers, such as divinylbenzene, divinyl naphthalene, andtrivinylbenzene; polyunsaturated alicyclic monomers, such as1,2,4-trivinylcyclohexane; di-functional esters of phthalic acid, suchas diallyl phthalate; polyunsaturated aliphatic monomers, such asdienes, trienes, and tetraenes, including isoprene, butadiene,1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene; and thelike.

Other suitable polyunsaturated crosslinking monomers include polyalkenylethers, such as triallyl pentaerythritol, diallyl pentaerythritol,diallyl sucrose, octaallyl sucrose, and trimethylolpropane diallylether; polyunsaturated esters of polyalcohols or polyacids, such as1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allylacrylate, diallyl itaconate, diallyl fumarate, diallyl maleate,trimethylolpropane tri(meth)acrylate, trimethylolpropanedi(meth)acrylate, and polyethylene glycol di(meth)acrylate; alkylenebisacrylamides, such as methylene bisacrylamide, propylenebisacrylamide, and the like; hydroxy and carboxy derivatives ofmethylene bis-acrylamide, such as N,N′-bismethylol methylenebisacrylamide; polyethyleneglycol di(meth)acrylates, such asethyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, andtriethyleneglycol di(meth)acrylate; polyunsaturated silanes, such asdimethyldivinylsilane, methyltrivinylsilane, allyldimethylvinylsilane,diallydimethylsilane and tetravinylsilane; polyunsaturated stannanes,such as tetraallyl tin, diallyldimethyl tin; and the like.

Useful monounsaturated compounds carrying a reactive group includeN-methylolacrylamide; N-alkoxy(meth)acrylamide, wherein the alkoxy groupis a C₁-C₁₈ alkoxy; and unsaturated hydrolyzable silanes, such astriethoxyvinylsilane, tris-isopropoxyvinylsilane, 3-triethoxysilylpropylmethacrylate, and the like.

Useful polyfunctional crosslinking monomers containing multiple reactivegroups include, but are not limited to, hydrolyzable silanes, such asethyltriethoxysilane and ethyltrimethoxysilane, epoxy-substitutedhydrolyzable silanes, such as2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and3-glycidoxypropyltrimethyoxysilane; polyisocyanates, such as1,4-diisocyanatobutane, 1,6-diisocyanatohexane,1,4-phenylenediisocyanate and 4,4′-oxybis(phenylisocyanate); unsaturatedepoxides, such as glycidyl methacrylate and allylglycidyl ether;polyepoxides, such as diglycidyl ether, 1,2,5,6-diepoxyhexane, andethyleneglycoldiglycidyl ether; and the like.

Particularly useful are polyunsaturated crosslinkers derived fromethoxylated polyols, such as diols, triols and bis-phenols, ethoxylatedwith about 2 to about 100 moles of ethylene oxide per mole of hydroxylfunctional group and end-capped with a polymerizable unsaturated group,such as a vinyl ether, allyl ether, acrylate ester, methacrylate ester,and the like. Examples of such crosslinkers include bisphenol Aethoxylated dimethacrylate; bisphenol F ethoxylated dimethacrylate,trimethylol propane ethoxylated trimethacrylate, and the like. Otherethoxylated crosslinkers useful in the ASAP polymers of the presentinvention include ethoxylated polyol-derived crosslinkers disclosed inU.S. Pat. No. 6,140,435 to Zanotti-Russo, the pertinent disclosures ofwhich are incorporated herein by reference.

Examples of particularly preferred crosslinkers are acrylate andmethacrylate esters of polyols having at least two acrylate ormethacrylate ester groups, such as trimethylolpropane triacrylate(TMPTA), trimethylolpropane dimethacrylate, polyethylene glycoldimethacrylate, ethoxylated (30) bisphenol A dimethacrylate (EOBDMA),and the like.

When utilized, crosslinking monomers are present in the monomer reactionmixture preferably in an amount in the range of about 0.01 to about 2weight percent, based on the total monomer mixture weight, morepreferably about 0.05 to about 1.5 weight percent, most preferably about0.1 to about 1 weight percent of the monomer mixture.

Chain Transfer Agent

The ASAP of the present invention can optionally be prepared from amonomer mixture comprising one or more chain transfer agents, which arewell known in the polymer arts.

Suitable chain transfer agents for use in this invention, without beinglimited thereto, are selected from a variety of thio and disulfidecontaining compounds, such as C₁-C₁₈ alkyl mercaptans,mercaptocarboxylic acids, mercaptocarboxylic esters, thioesters, C₁-C₁₈alkyl disulfides, aryldisulfides, polyfunctional thiols, and the like;phosphites and hypophosphites; haloalkyl compounds, such as carbontetrachloride, bromotrichloromethane, and the like; and unsaturatedchain transfer agents, such as alpha-methylstyrene.

Polyfunctional thiols include trifunctional thiols, such astrimethylolpropane-tris-(3-mercaptopropionate), tetrafunctional thiols,such as pentaerythritol-tetra-(3-mercaptopropionate),pentaerythritol-tetra-(thioglycolate), andpentaerythritol-tetra-(thiolactate); hexafunctional thiols, such asdipentaerythritol-hexa-(thioglycolate); and the like.

Alternatively, the chain transfer agent can be any catalytic chaintransfer agent which reduces molecular weight of addition polymersduring free radical polymerization of vinyl monomers. Examples ofcatalytic chain transfer agents include, for example, cobalt complexes(e.g., cobalt (II) chelates). Catalytic chain transfer agents can oftenbe utilized in relatively low concentrations relative to thiol-basedCTAs.

Examples of preferred chain transfer agents include octyl mercaptan,n-dodecyl mercaptan (DDM), t-dodecyl mercaptan, hexadecyl mercaptan,octadecyl mercaptan (ODM), isooctyl 3-mercaptopropionate (IMP), butyl3-mercaptopropionate, 3-mercaptopropionic acid, butyl thioglycolate,isooctyl thioglycolate, dodecyl thioglycolate, and the like. The chaintransfer agents can be added to a monomer reaction mixture preferably inamounts of up to about 10 weight percent of polymerizable monomermixture, based on total monomer mixture weight.

The inventive ASAP can be manufactured by conventional polymerizationtechniques, such as emulsion polymerization, as is known in the polymerart. Typically the polymerization process is carried out at a reactiontemperature in the range of about 30 to about 95° C., however, higher orlower temperatures can be used. To facilitate emulsification of themonomer mixture, the emulsion polymerization can be carried out in thepresence of anionic surfactants, such as fatty alcohol sulfates or alkylsulfonates, nonionic surfactants, such as linear or branched alcoholethoxylates, amphoteric surfactants, or mixtures thereof. The emulsionpolymerization reaction mixture also includes one or more free radicalinitiators, preferably in an amount in the range of about 0.01 to about3 weight percent based on total monomer weight. The polymerization canbe performed in an aqueous or aqueous alcohol medium at a low pH, i.e.,preferably not more than about pH 4.5.

Anionic surfactants suitable for facilitating emulsion polymerizationsare well known in the polymer art, and include sodium lauryl sulfate,sodium dodecyl benzene sulfonate, disodium laureth-3 sulfosuccinate,sodium dioctyl sulfosuccinate, sodium di-sec-butyl naphthalenesulfonate, disodium dodecyl diphenyl ether sulfonate, disodiumn-octadecyl sulfosuccinate, phosphate esters of branched alcoholethoxylates, and the like.

Exemplary free radical initiators include, without being limitedthereto, the water-soluble inorganic persulfate compounds, such asammonium persulfate, potassium persulfate, and sodium persulfate;peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide,and lauryl peroxide; organic hydroperoxides, such as cumenehydroperoxide and t-butyl hydroperoxide; organic peracids, such asperacetic acid and perbenzoic acid (optionally activated with reducingagents, such as sodium bisulfite or ascorbic acid); and oil soluble,free radical producing agents, such as 2,2′-azobisisobutyronitrile, andthe like. Particularly suitable free-radical polymerization initiatorsinclude water soluble azo polymerization initiators, such as2,2′-azobis(tert-alkyl) compounds having a water solubilizingsubstituent on the alkyl group. Preferred azo polymerization catalystsinclude the VAZO® free-radical polymerization initiators, available fromDuPont, such as VAZO® 44 (2,2′-azobis(2-(4,5-dihydroimidazolyl)propane),VAZO® 56 (2,2′-azobis(2-methylpropionamidine) dihydrochloride), andVAZO® 68 (4,4′-azobis(4-cyanovaleric acid)).

Optionally, other emulsion polymerization additives, which are wellknown in the emulsion polymerization art, such as buffering agents,chelating agents, inorganic electrolytes, chain terminators, and pHadjusting agents can be included in the polymerization system.

A preferred general emulsion polymerization procedure for thepreparation of alkali-swellable or alkali-soluble associated polymers ofthe present invention is provided below:

A monomer emulsion is prepared in a first reactor equipped with anitrogen inlet and an agitator, by combining a desired amount of eachmonomer in water containing an emulsifying amount of an anionicsurfactant under a nitrogen atmosphere and with mixing agitation. To asecond reactor equipped with an agitator, nitrogen inlet and feed pumps,are added a desired amount of water and additional anionic surfactant,if desired, under a nitrogen atmosphere, and the contents of the secondreactor are heated with mixing agitation. After the contents of thesecond reactor reach a temperature in the range of about 65-98° C., afree radical initiator is injected into the so-formed aqueous surfactantsolution in the second reactor, and the monomer emulsion from the firstreactor is then gradually pumped into the second reactor over a periodof typically in the range of about one to about four hours at acontrolled reaction temperature in the range of about 65-95° C. Aftercompletion of the monomer addition, an additional quantity of freeradical initiator can be added to the second reactor, if desired, andthe resulting reaction mixture is typically held at a temperature ofabout 75-95° C. for a time period sufficient to complete thepolymerization reaction. The resulting polymer emulsion can then becooled and discharged from the reactor.

One skilled in the polymer arts will recognize that the amounts of eachmonomer component can be adjusted to obtain polymers having any desiredratio of monomers. Larger or smaller proportions of water may also beutilized, as desired. Water miscible solvents, such as alcohols, andother polymerization additives, as described above, may also be includedin the reaction mixture. Nonionic surfactants, such as linear orbranched alcohol ethoxylates, can also be added as is known in theemulsion polymerization art.

The product polymer emulsions can be prepared to preferably containabout 1 percent to about 60 percent total polymer solids, morepreferably about 10 percent to about 50 percent total polymer solids,most preferably about 15 percent to about 45 percent total polymersolids (TS) based on the weight of the polymer.

Prior to any neutralization, the polymer emulsions, as produced,typically have a pH in the range of about 2 to not more than about 5.5,a Brookfield viscosity of not more than about 100 milli-Pascal seconds(mPa·s) at ambient room temperature (spindle #2, 20 rpm) and a glasstransition temperature (Tg) of not more than about 150° C. as determinedby Method C below.

Optionally, the produced polymer emulsions can be further processed byadjusting the pH to a value preferably in the range of about 3 to about7.5 or greater, if an alkaline pH is desired, with alkaline materials,preferably alkali metal hydroxides, organic bases, and the like. Thepolymer emulsions typically swell to a viscosity greater than about 100mPa·s and form viscous solutions or gels at neutral to alkaline pH, andthe polymers are generally substantially stable at such pH values, evenat pH values greater than about 12. The polymer emulsions can be dilutedwith water or solvent, or concentrated by evaporation of a portion ofthe water. Alternatively, the obtained polymer emulsion may besubstantially dried to a powder or crystalline form by utilizingequipment well known in the art, such as, for example, a spray drier, adrum drier, or a freeze drier.

The inventive ASAP can be prepared by emulsion polymerization andutilized by incorporating various known additives and conventionaladjuvants, and solvents other than water, into the ASAP emulsionproduct, as needed, to achieve the intended form for use of the finalcomposition without altering or adversely affecting the performance orproperties of the ASAP. Alternatively, the ASAP can be incorporated asan ingredient into a formulation, preferably in a liquid form, employingconventional mixing equipment.

The ASAP of this invention can be employed as a film former. When theglass transition temperature (Tg) of a selected ASAP film former issubstantially above ambient room temperature, the Tg of the ASAP filmformer can be adjusted to achieve a desired Tg by including additives inthe formulation, such as coalescing agents, plasticizers and mixturesthereof. Such additives can assist in film formation by lowering the Tgof the ASAP to the ambient room temperature or desired temperature.

The inventive ASAP can be utilized, for example, without being limitedthereto, as a rheology modifier, suspending agent, film former,thickener, stabilizer, emulsifier, solubilizer, and the like, informulated compositions for personal care products, topical health careproducts, household care products, institutional and industrial (I&I)products and industrial processes. The foregoing products can typicallycontain various additives and conventional adjuvants as are well knownin the art, including, without being limited thereto, acidifying oralkalizing pH adjusting agents and buffering agents; fixatives and filmformers, such as gums, resins, polymers of synthetic or natural origin,and the like; auxiliary rheology modifiers, such as viscosity-increasingpolymeric thickeners or gellants, additives, such as emulsifiers,emulsion stabilizers, waxes, dispersants, and the like, and viscositycontrol agents, such as solvents, electrolytes, and the like; hair andskin conditioning agents, such as antistatic agents, synthetic oils,vegetable or animal oils, silicone oils, monomeric or polymericquaternized ammonium salts, emollients, humectants, lubricants,sunscreen agents, and the like; chemical hair waving or straighteningagents; hair colorants, such as pigments and dyes for temporary,semipermanent, or permanent hair dyeing; surfactants, such as anionic,cationic, nonionic, amphoteric and zwitterionic surfactants; polymerfilm modifying agents, such as plasticizers, humectants, tackifiers,detackifiers, wetting agents and the like, product finishing agents,such as chelating agents, opacifiers, pearlescing agents, preservatives,fragrances, solubilizers, colorants, such as pigments and dyes, UVabsorbers, and the like; propellants (water-miscible orwater-immiscible), such as fluorinated hydrocarbons, liquid volatilehydrocarbons, compressed gases, and the like; and mixtures thereof.

In one preferred embodiment, an aqueous gel formulation comprising anASAP of the present invention also includes a C₁-C₈ monohydric alcoholsuch as methanol, ethanol, isopropanol, hexanol, benzyl alcohol, and thelike, or a C₃-C₈ polyol such as ethylene glycol, propylene glycol,glycerin, hexylene glycol, butylene glycol, inositol, sorbitol,mannitol, and the like. The amount of ASAP employed is not limited, aslong as the purpose and properties of the compositions containing theASAP perform their intended function. A useful amount of active weightpercent ASAP can be in the range of about 0.01% to about 25%, preferablyabout 0.05% to about 20%; more preferably about 0.1% to about 15%.

In a preferred alkali-swellable ASAP embodiment, a concentration ofabout 1 active weight % ASAP in deionized water, in its neutralized oranionic form at a pH in the range of about 3 to about 9, can provide aBrookfield viscosity ranging from about 100 mPa·s to 100,000 mPa·s ormore (Brookfield RVT, 20 rpm, at about 25° C. ambient room temperature).In a preferred alkali-soluble ASAP embodiment, a concentration of about5 active weight % ASAP in deionized water or in a hydroalcoholic medium,in its neutralized form at a pH in the range of about 5.5 to about 8.5provides a Brookfield viscosity preferably of not more than about 1000mPa·s.

While the ASAP minimize or eliminate the need for added thickeners, theASAP can be used in combination with conventional polymeric thickeners,such as natural gums, resins, polysaccharides, synthetic polymericthickeners, and the like, popularly used in the art. It is known thatthe viscosity obtained with anionic polymers, such as alkali-swellablecarbomer polymer, commonly employed as a thickener or as a drug carrierin medicaments, can be negatively affected by the presence of anionicpolymer. Surprisingly, it was found that the ASAP were compatible witheither traditional carbomer polymer or with hydrophobically-modifiedcarbomer polymer and the viscosity produced by such combinations wasunexpectedly higher than the sum of the viscosities of alkali-swellableASAP and carbomer polymer by themselves at the same concentrations. Thisbeneficially allows the use of alkali-swellable ASAP in formulationscontaining carbomer polymer or hydrophobically modified carbomerpolymer, if desired, to further enhance the aesthetic and rheologicalproperties of the formulation.

Concentrated additives, adjuvant ingredients, products or materials thatcan be employed with the inventive polymers are referred to herein bythe international nomenclature commonly known to as INCI name given themin the International Cosmetic Ingredient Dictionary, Volumes 1 and 2,Sixth Edition, (1995), or International Cosmetic Ingredient Dictionaryand Handbook, Volumes 1-3, Seventh Edition, (1997), both published bythe Cosmetic, Toiletry, and Fragrance Association, Washington D.C. (bothhereafter INCI Dictionary), or by their commonly used chemical names.Numerous commercial suppliers of materials that can be employed, listedby INCI name, trade name or both can be found in the INCI Dictionary andin numerous commercial trade publications, including but not limited tothe 2001 McCutcheon's Directories, Volume 1: Emulsifiers & Detergentsand Volume 2: Functional Materials, published by McCutcheon's Division,The Manufacturing Confectioner Publishing Co. Glen Rock, N.J. (2001);and 2001 Cosmetic Bench Reference, edition of COSMETICS & TOILETRIES®115 (13), published by Allured Publishing Corporation, Carol Stream,Ill. (2001); the relevant disclosures of the INCI Dictionary and each ofthe foregoing publications being incorporated herein by reference.

Compositions for personal care and topical health care can comprise anycosmetic, toiletry, and topical pharmaceutical formulation that requiresrheology modification or thickening known from the cosmetic andpharmaceutical literature. Typical personal care formulations that caninclude the ASAP as a rheology modifier include, without being limitedthereto, shampoos, chemical and non-chemical hair curling and hairstraightening products, hair style maintenance products, emulsionlotions and creams for the nails, hands, feet, face, scalp, and body,hair dyes, face and body makeup, nail care products, astringents,deodorants, antiperspirants, depilatories, skin-protective creams andlotions, such as sunscreens, skin and body cleansers, skin conditioners,skin toners, skin firming compositions, liquid soaps, soap bars, bathproducts, shaving products, and the like. Formulated compositions fortopical health care that are applied to the skin and mucous membranesfor cleansing or soothing are compounded with many of the samephysiologically tolerable cosmetic ingredients and chemically inertingredients employed for personal care products in the same productforms, differing primarily in the purity grade of ingredients and by thepresence of topically active medicaments. For example, topical healthcare products include oral hygiene products, such as toothpastes, oralsuspensions, and mouth care products, which can be classified aspharmaceuticals or over-the-counter products, and includepharmacosmetics, which contain phytopharmaceutic or nutraceuticalingredients.

Compositions for personal care and topical health care can be in theform of, without being limited thereto, liquids, such as rinses, gels,sprays, emulsions, such as lotions and creams, shampoos, pomades, foams,ointments, tablets, sticks, such as lip care products, makeup, andsuppositories, and like products, which are applied to skin and hair andremain in contact therewith until removed as by rinsing with water orwashing with shampoo or soap. Gels can be soft, stiff, or squeezable.Emulsions can be oil-in-water, water-in-oil, or multiphase. Sprays canbe non-pressurized aerosols delivered from manually pumpedfinger-actuated sprayers or can be pressurized aerosols. The ASAP can beformulated in an aerosol composition, such as in a spray, mousse, orfoam forming formulation, where a chemical or gaseous propellant isrequired. Physiologically and environmentally tolerable propellants,such as compressed gases, fluorinated hydrocarbons and liquid volatilehydrocarbons, and the amounts and suitable combinations to be used, arewell known in the cosmetic and pharmaceutical art and literature.

An extensive listing of personal care and cosmetic ingredients and theirfunctions, for example, appears in the INCI Dictionary, generally, andin Vol. 2, Section 4 of the Seventh Edition, in particular, incorporatedherein by reference. Those skilled in the art of formulating personalcare and health care products recognize that some ingredients aremultifunctional and, hence, can serve more than one purpose in theformulation. Thus, the amount of ASAP polymer employed as a personalcare or health care product component is not limited, as long as thepurpose and properties of the formulated composition performs itsintended function.

Typical household care, and I&I care products that can contain ASAP as arheology modifier include, without being limited thereto, surfacecleansers for kitchen and bathroom counter tops, tiled surfaces, andutilities, including appliances employed or located therein, toiletcleaners, including toilet bowl rim gels, floor cleansers, wallcleansers, polishes, air freshener gels, detergents, treatments andcleansers for dishes and laundry, such as fabric softener, spot reducer,fabric treatments, and the like.

The ASAP are suitable for use as rheology modifiers in industrialprocesses and applications. For example, the ASAP can be employed intextile treatments as processing and finishing aids for textile coating,printing and finishing formulations, inks, metal cleaners, scaleremovers, paint and varnish strippers, polishes for furniture, shoes,cars, or metal, and the like.

Thus, compositions containing ASAP can be in any form, including but notlimited to, a liquid, a gel, a spray, an emulsion, a semisolid, such asa paste, a solid, such as a stick, tablet or bar, and the like, so longas the composition is useful for its intended function.

The following examples further illustrate the preparation and use ofpreferred embodiments but are not intended to be limiting.

Materials and Procedures

The materials are generally commercially available from chemical supplyhouses known to those skilled in the chemical arts or from the supplierindicated.

1. Materials Abbreviations and Trade Names

-   EA Ethyl acrylate-   WAM Methacrylamidoethyl-N-ethyleneurea (SIPOMER® WAM II, Rhodia,    Inc.)-   MAA Methacrylic acid-   MMA Methyl methacrylate-   AA Acrylic acid-   SSSA Sodium salt of styrene sulfonic acid-   BEM25 Beheneth-25 methacrylate-   LEM23 Laureth-23 methacrylate-   CSEM25 Ceteareth-25 methacrylate-   HCOEM25 Hydrogenated castor oil ethoxylated (25) methacrylate-   HCOEM16 Hydrogenated castor oil ethoxylated (16) methacrylate-   TEM25 Tristyrylphenol ethoxylated (25) methacrylate-   CHEM24 Choleth-24 methacrylate-   CEM24 Ceteth-24 methacrylate-   EOBDMA Ethoxylated (30) bisphenol A dimethacrylate-   TMPTA Trimethylolpropane triacrylate-   IMP Isooctyl 3-mercaptopropionate-   DDM Dodecyl mercaptan-   ODM Octadecyl mercaptan-   R307A randomly ethoxylated/propoxylated 1,4-butanediol vinyl ether    having the empirical formula CH₂═CH—O—(CH₂)₄—O—(C₃H₆O)₄—(C₂H₄O)₃₀—H    (EMULSOGEN® R307, Clariant Corporation)-   BX-AA A randomly ethoxylated/propoxylated allyl ether having the    empirical formula CH₂═CH—CH₂—O—(C₃H₆O)₅—(C₂H₄O)₅—H (BX-AA-E5P5,    Bimax, Inc.)-   M5010 A carboxy-functional C₁₂-C₁₅ alkenyl hydrophobe, ethoxylated    with about 24 ethylene oxide units (MAXEMUL® 5010, Uniqema)-   MPEG35 Methoxy ethoxylated (35) methacrylate-   MPEG55 Methoxy ethoxylated (55) methacrylate    2. Methods.

A. Viscosity. The reported viscosity of each polymer containingcomposition was measured in milli-Pascal seconds (mPa·s), employing aBrookfield rotating spindle viscometer, (Brookfield, Model RVT) at about20 revolutions per minute (rpm), at ambient room temperature of about20-25° C. (hereafter referred to as Brookfield viscosity). Viscosity wasmeasured on freshly prepared compositions (referred to as “initialviscosity”, and re-measured after allowing the composition to age for atleast about 24 hours at ambient room temperature (referred to as“24-hour viscosity”). Where only one viscosity value is shown below, theviscosity value is the 24-hour viscosity, unless otherwise indicated.

A “thin viscosity” typically refers to a pourable, runny, sprayable,product having a viscosity of up to about 1,000 mPa·s; a “mediumviscosity” refers to a product having a viscosity in the range of above1,000 to about 3,000 mPa·s; a “high viscosity” refers to a producthaving a viscosity in the range of above 3,000 to about 10,000 mPa·s;and gel refers to a product having a viscosity greater than 10,000mPa·s, unless otherwise indicated.

B. Clarity. When reported, the clarity of the polymer-containingcomposition was measured in % T (transmittance) by Brinkmann PC 920calorimeter at least about 24 hours after the composition was made.Clarity measurements were taken against deionized water (clarity ratingof 100%). Compositions having a clarity of about 60% or more weresubstantially clear; compositions having a clarity in the range of about45-59% were judged substantially translucent.

C. Glass transition temperature. When reported, the glass transitiontemperature (Tg) of the associative polymer was determined by casting aportion of the product emulsion on a MYLAR® (polyethylene terephthalate)film substrate using a 10 mil opening draw-down bar, drying the castfilm at ambient room temperature (about 25° C.) for about 24 hours, andthen measuring the T_(g) by well known Differential Scanning Calorimetry(DSC) technique.

D. Gloss. When reported, the gloss of the associative polymer film wasdetermined by casting a film of the polymer product on a Leneta Form2C-opacity chart (Leneta Co.) using a 10 mil opening draw down bar,drying the cast film at about 25° C. (about 77° F.) for about 24 hours,and then instrumentally measuring the specular gloss of the dried filmat a reflectance angle of 20° and 60° geometry employing aMicro-Tri-Gloss glossmeter, (Byk/Gardner, Silver Spring, Md.) using theStandard Test Method for Specular Gloss, ASTM 523-89 (Reapproved 1994).A specular gloss value of 100 units was assigned to the standard foreach geometry. A specular gloss value unit reading of at least about 30at an angle of 20° and at least about 80 at an angle of 60° was judgedglossy and a value of less than 25 at either angle was judged dull.

E. Turbidity. When reported, the turbidity of a polymer-containingcomposition was determined in Nephelometric Turbidity Units (NTU)employing a nephelometric turbidity meter with distilled water (NTU=0)as the standard. Compositions having an NTU value of about 90 or greaterwere judged turbid.

F. Humidity Resistance—Percent curl retention. The resistance of apolymer to high humidity (about 90% Relative Humidity (RH)) was measuredby its ability to hold a curl set on hair after absorption of water fromthe applied composition and from the surrounding atmosphere employingthe well known technique commonly referred to as high humidity curlretention (HHCR). Descriptions of the HHCR methodology are readily foundin the cosmetic literature. See, for example, Ch. 30, Harry'sCosmeticology, 8th Ed., M. J. Rieger, Ph.D. (ed.), 666-667, ChemicalPublishing Co., Inc., New York, N.Y. (2000), and Diaz et al., J. Soc.Cosmet. Chem., 34, 205-212 (July 1983), the relevant disclosures of eachare incorporated herein by reference.

Tresses of commercially blended Caucasian untreated (virgin) human hairwere prepared employing natural brown or black color European hairsupplied by International Hair Importers and Products Inc., New York.Each hair tress (about 3 grams weight) was about 7 inches (about 18 cm)in length and was anchored with glue at the scalp (root) end portion.Prior to use, each hair tress was pre-cleaned by washing with a diluteaqueous solution of sodium lauryl sulfate (10% SLS), followed bythorough rinsing with deionized water at ambient room temperature anddried with towel blotting. The initial extended length of the hair(L_(e)) was measured. About 0.8 grams of polymer-containing compositionto be evaluated was applied to the hair tress and distributed uniformlyfrom the scalp to end portion. The treated hair tress was then wrappedaround a hair curler having an outer diameter of about 3 cm, and driedon the curler overnight at an ambient room temperature of about 21-23°C. (about 71-73° F.). After drying, the curler was carefully removed,leaving the hair styled into a single curl, the initial length of thehair curl (L_(i)) was measured, and the curled hair tress was verticallyhung in a humidity chamber set at an ambient temperature of about 26-27°C. and ambient high humidity of about 90% RH.

The resistance to high humidity, based on percent curl retention (HHCR)was determined by measuring the length of the hair curl as the curlrelaxed after selected intervals (L_(t)) of exposure to humidity. Thefollowing equation was used to calculate percent curl retention,relative to the initial curl length (L_(i)) and length of the fullyextended hair, before curling (L_(e)).

${\%\mspace{14mu}{Curl}\mspace{14mu}{Retention}} = {\frac{L_{e} - L_{t}}{L_{e} - L_{i}} \times 100}$

The change in curl length (droop, helix formation) was periodicallymeasured and monitored over a period in the range of about 4 to about 24hours with a final reading being taken after about 24 hours. A retentionof about 70% or more curl (HHCR) for a minimum period of about 0.75hours at about 90% RH is a conventional benchmark for good high humidityresistance, and an HHCR greater than 70% after a period of at leastabout 3 hours is judged very good to excellent.

G. Subjective Properties Assessment. The tactile, aesthetic andmechanical properties of hair treated with polymer-containingcomposition, such as feel, flaking, ease of combing, curl memory, suchas bouncy/curl-up, and static flyaway were subjectively assessed. Feelwas assessed by the psychosensory tactile characteristics of thepolymer-containing product (tackiness, smoothness, and the like) whilebeing hand applied to hair. Flaking of polymer on the hair, if any, wasassessed by inspecting the hair for visible deposit (coating) on thehair surface and by combing the treated hair and then inspecting thetines of the comb for visible residue. Combing ease and static flyawayof the hair was subjectively assessed during combing by noting hairtangles, flyaway fibers and difficulty in combing through the hair. Curlmemory was subjectively assessed by observing the bouncy, curl-upappearance of the hair curl pattern (i.e., complete curl, open helix orspiraling or loss of curl) remaining in the hair after exposure to highhumidity of about 90% RH.

H. Methods of Preparing Associative Polymers. A general emulsionpolymerization procedure preparation of alkali-swellable associativepolymers of the present invention is provided below:

A monomer emulsion is prepared in a first reactor equipped with anitrogen inlet and an agitator, by combining a desired amount of eachmonomer in water containing an emulsifying amount of an anionicsurfactant under a nitrogen atmosphere, with mixing agitation. To asecond reactor equipped with a mixing agitator, nitrogen inlet and feedpumps, are added a desired amount of water and additional anionicsurfactant, if desired, and the contents are heated under a nitrogenatmosphere with mixing agitation. After the second reactor reaches atemperature in the range of about 80-90° C., a desired amount of a freeradical initiator is injected into the surfactant solution in the secondreactor, and the monomer emulsion from the first reactor is thengradually pumped into the second reactor over a period in the range ofabout one to about four hours at a controlled reaction temperature inthe range of about 80-90° C. After completion of the monomer addition,an additional quantity of free radical initiator can be added to thesecond reactor, if desired, and the resulting reaction mixture is heldat a temperature of about 90-95° C. for a time period sufficient tocomplete the polymerization reaction, typically about 90 minutes. Theresulting polymer emulsion can then be cooled and discharged from thereactor.

I. Methods for Preparing Polymer-Containing Compositions. Forillustration, and not by limitation, product ASAP emulsions preparedaccording to the general Method H above were employed for preparing thecompositions in the following examples. Unless otherwise indicated, theproduct ASAP emulsions were diluted with water to obtain the desiredpolymer concentration or were added to a formulation with the watersoluble ingredients in an amount sufficient to provide the desiredpolymer concentration in the finished formulation. All references toweight % polymer means active weight % polymer on a total formulationweight basis. Unless otherwise indicated, formulations are preparedemploying conventional formulation techniques well known to thoseskilled in the formulation arts. The inventive polymers were suitablefor use as rheology modifiers, film-formers, thickeners, suspendingagents and the like as illustrated in the following examples.

EXAMPLE 1 Polymers

The alkali-swellable associative polymer, identified as Polymer A inTable 2A, was prepared according to the general procedure described asMethod H, and as described in detail below.

A monomer reaction mixture was prepared in a first reactor, under anitrogen atmosphere, using an agitator mixer rotating at about 500 rpm,by combining about 117 parts by weight of methacrylic acid, about 172parts by weight of ethyl acrylate, about 25.5 parts by weight of BEM25,and about 3.2 parts by weight of LEM23 into about 92 parts by weight ofdeionized water containing about 10.6 parts by weight of 30% aqueoussodium lauryl sulfate. To a second reactor, equipped with a mixingagitator, nitrogen inlet and feed pumps, were added about 570 parts byweight of deionized water and about 3.2 parts by weight of 30% aqueoussodium lauryl sulfate. The contents of the second reactor were heatedwith mixing agitation at a rotation speed of about 200 rpm under anitrogen atmosphere. After the contents of the second reactor reached atemperature in the range of about 85-88° C., about 6.3 parts of 3.5%ammonium persulfate solution (a free radical initiator) was injectedinto the so-formed hot surfactant solution in the second reactor. Theaqueous emulsion of the monomer mixture from the first reactor wasgradually pumped into the second reactor over a period of about 60minutes at a controlled reaction temperature in the range of about85-88° C. At the completion of the monomer mixture addition, about 9.4parts by weight of 0.7% ammonium persulfate solution was added to thereaction mixture in the second reactor and the temperature of thereaction was maintained at about 90° C. for an additional one and halfhours to complete polymerization. The resulting ASAP emulsion was cooledto room temperature, discharged from the reactor and collected.

Comparative HASE Polymers, CP-1 through CP-6, each having the monomercomponents shown in Table 1, the inventive alkali-swellable ASAP,Polymers B-M, N-Z and AA-AW, and alkali-soluble ASAP, Polymers BA-BL,each having the monomer components shown, respectively, in Tables 2A,2B, 2C, and 2D, respectively, were prepared following the general methodfor the preparation of Polymer A, above. All monomers listed for a givenpolymer, were included in the monomer reaction mixture in the firstreactor and the amounts of the monomers were adjusted, as needed, toachieve the monomer weight percent values listed in Tables 1, 2A, 2B,and 2C; all % values in the tables are weight percent, based on totalmonomer mixture weight.

All of the polymers were prepared as aqueous solutions having totalsolids levels in the range of about 30 to about 45%. In most cases,sodium lauryl sulfate (SLS) was utilized as the emulsifying surfactantfor the polymerization reaction. In addition, Polymer AV was alsosuccessfully prepared according to the foregoing procedure utilizing acombination of SLS and nonionic emulsifying surfactant, i.e.,Ceteareth-20 (INCI name for polyoxyethylene (20) cetyl/stearyl ether).In the preparations of Polymers BH, BK, and BL, the followingsurfactants were utilized in place of SLS, respectively: RHODAFAC® 610(a complex phosphate ester of a branched alcohol ethoxylate, availablefrom Rhodia, Inc., Cranbury, N.J.), disodium laureth-3-sulfosuccinate,and sodium dioctyl sulfosuccinate.

TABLE 1 Comparative HASE Polymer Compositions Acidic Vinyl AssociativePolymer Monomer Nonionic Vinyl Monomer(s) Other No. (%) Monomer (%) (%)Monomer(s) (%) CP-1 MAA (37) EA (53.7) BEM25 (9) EOBDMA (0.3) CP-2 MAA(37) EA (53) BEM25 (10) CP-3 MAA (37) EA (59.7) BEM25 (3) TMPTA (0.3)CP-4 MAA (37) EA (53.55) BEM25 (8); EOBDMA (0.3); CSEM25 (1) IMP (0.15)CP-5 MAA (36) EA (60.9) BEM25 (3) TMPTA (0.1) CP-6 MAA (37) EA (53.7)BEM25 (9) Diallyl phthalate (0.3)

TABLE 2A Inventive Polymer Compositions Acidic Vinyl Nonionic VinylAssociative Optional Poly. Monomer(s) Monomer(s) Monomers Monomer(s) No.(%) (%) (%) (%) A MAA (37) EA (54) BEM25 (8); LEM23 (1) B MAA (34); EA(55.85); BEM25 (4); TMPTA (0.1); AA (2) WAM (3) LEM23 (1) EOBDMA (0.05)C MAA (37) EA (53.7) BEM25 (8); EOBDMA (0.3) LEM23 (1) D MAA (37) EA(53.7) BEM25 (8); EOBDMA (0.3) HCOEM25 (1) E MAA (37) EA (53.7) BEM25(8); EOBDMA (0.3) HCOEM16 (1) F MAA (37) EA (53.7) BEM25 (8); EOBDMA(0.3) TEM25 (1) G MAA (37) EA (53.85) BEM25 (8); IMP (0.15) LEM23 (1) HMAA (37) EA (53.55) BEM25 (8); EOBDMA (0.3); LEM23 (1) IMP (0.15) I MAA(37) EA (53.85) BEM25 (8); ODM (0.15) LEM23 (1) J MAA (37) EA (53.55)BEM25 (8); ODM (0.15) LEM23 (1) EOBDMA (0.3) K MAA (37) EA (57.9) BEM25(4); TMPTA (0.1) LEM23 (1) L MAA (37) EA (53.7) BEM25 (6); EOBDMA (0.3)LEM23 (3) M MAA (37) EA (57.7) BEM25 (4); TMPTA (0.15); LEM23 (1) EOBDMA(0.15)

TABLE 2B Inventive Polymer Compositions Nonionic Acidic Vinyl VinylAssociative SH Optional Monomer Monomer Monomer(s) Monomer(s) Monomer(s)Poly. No. (%) (%) (%) (%) (%) N MAA (37) EA (59.7) CHEM24 (1.5); EOBDMA(0.3) CEM24 (1.5) O MAA (37) EA (56.7) BEM25 (3); EOBDMA (0.3) CHEM24(1.5); CEM24 (1.5) P MAA (37) EA (59.9) BEM25 (2); TMPTA (0.1) LEM23 (1)Q MAA (36) EA (58.1) BEM25 (2); R307 (2.8) TMPTA (0.1) LEM23 (1) R MAA(35) EA (58.9) BEM25 (2); M5010 (3) TMPTA (0.1) LEM23 (1) S MAA (35) EA(56.9) BEM25 (2); R307 (3); TMPTA (0.1) LEM23 (1) M5010 (2) T MAA (37)EA (42.8) BEM25 (15); TMPTA (0.05); LEM23 (5) EOBDMA (0.15) U MAA (37)EA (57.8) BEM25 (4); TMPTA (0.2) LEM23 (1) V MAA(37) EA (53.7) BEM25(3); EOBDMA (0.3) LEM23 (6) W MAA (37) EA (53.7) BEM25 (4.5); EOBDMA(0.3) LEM23 (4.5) X MAA (36) EA (55.9) BEM25 (2); BX-AA (5) TMPTA (0.1)LEM23 (1) Y MAA (36) EA (54.9) BEM25 (3); R307 (5) TMPTA (0.1) LEM23 (1)Z MAA (36) EA (55.9) BEM25 (2); R307 (5) TMPTA (0.1) LEM23 (1)

TABLE 2C Inventive Polymer Compositions Nonionic Acidic Vinyl VinylAssociative SH Optional Monomer(s) Monomer(s) Monomer(s) Monomer MonomerPoly. No. (%) (%) (%) (%) (%) AA MAA (37); EA (51) BEM25 (6); SSSA (5)LEM23 (1) AB MAA (36) EA (55.2) BEM25 (2.5); R307 (5) EOBDMA (0.3)CHEM24 (0.5); CEM24 (0.5) AC MAA (52); EA (42.7) BEM25 (2); EOBDMA (0.3)AA (2) LEM23 (1) AD MAA (36) EA (48.7) BEM25 (10); EOBDMA (0.3) LEM23(5) AE MAA (37) EA (59.7) BEM25 (2); EOBDMA (0.3) LEM23 (1) AF MAA (36)EA (58.4) BEM25 (3) R307 (2.5) TMPTA (0.1) AG MAA (36) EA (55.9) BEM25(3) R307 (5) TMPTA (0.1) AH MAA (36) EA (53.4) BEM25 (3) R307 (7.5)TMPTA (0.1) AI MAA (36) EA (45.9) BEM25 (3) R307 (15) TMPTA (0.1) AJ MAA(37) EA (53.7) BEM25 (8) MPEG35 (1) EOBDMA (0.3) AK MAA (37) EA (53.7)BEM25 (8) MPEG55 (1) EOBDMA (0.3) AL MAA (2.5); EA (57.5) BEM25 (8)MPEG55 (1) AA (31) AM MAA (36) EA (57.9) BEM25 (2); R307 (3) TMPTA (0.1)CHEM24 (0.5); CEM24 (0.5) AN MAA (35) EA (56.9) BEM25 (4); M5010 (3)TMPTA (0.1) LEM23 (1) AO MAA (36) EA (52.9) BEM25 (4); BX-AA (3) TMPTA(0.1) WAM (3) LEM23 (1) AP MAA (36) EA (50.9) BEM25 (4); BX-AA (5) TMPTA(0.1) WAM (3) LEM23 (1) AQ MAA (36) EA (53.85) BEM25 (4); BX-AA (5)TMPTA (0.15) LEM23 (1) AR MAA (37) EA (48.8) CSEM25 (9) BX-AA (5) TMPTA(0.2) AS MAA (36) EA (54.7) BEM25 (8); TMPTA (0.3) LEM23 (1) AT MAA (37)EA (51.8) CSEM25 (10) BX-AA (1) TMPTA (0.2) AU MAA (37) EA (51.8) CSEM25(10) R307 (1) TMPTA (0.2) AV MAA (37) EA (52.8) CSEM25 (8) BX-AA (2)TMPTA (0.2) AW MAA (47) EA (46.8) CSEM25 (4) BX-AA (2) TMPTA (0.2)

TABLE 2D Inventive Polymer Compositions Nonionic Chain Acidic VinylVinyl Associative Transfer Poly. Monomer(s) Monomer(s) Monomer(s) SHMonomer Agent No. (%) (%) (%) (%) (%) BA MAA (29); EA (43.2); BEM25(2.5); R307 (2); DDM (0.8) MMA (19.5) LEM23 (1) M5010 (2) BB MAA (28.64)EA (44.44); BEM25 (2.47) R307 (1.975); DDM (1.24) MMA (19.26) M5010(1.975) BC MAA (28.64) EA (44.44); LEM25 (2.47) R307 (1.975); DDM (1.24)MMA (19.26) M5010 (1.975) BD MAA (28.64) EA (44.44); CSEM25 (2.47) R307(1.975); DDM (1.24) MMA (19.26) M5010 (1.975) BE MAA (25) EA (47.74)BEM25 (2.5) R307 (2); DDM (1.26) MMA (19.5) M5010 (2) BF MAA (29) EA(43.74) LEM25 (2.5) R307 (2); DDM (1.26) MMA (19.5) M5010 (2) BG MAA(29) EA (43.74) CSEM25 (2.5) R307 (2); DDM (1.26) MMA (19.5) M5010 (2)BH MAA (24.78) EA (48.56) BEM25 (2.48) R307 (1.98); DDM (0.89) MMA(19.33) M5010 (1.98) BI MAA (25) EA (50.74) BEM25 (2.5) M5010 (1) DDM(1.26) MMA (19.5) BJ MAA (25) EA (50.74) BEM25 (2.5) BX-AA (1) DDM(1.26) MMA (19.5) BK MAA (17.5) EA (52.74) BEM25 (2.5) BX-AA (1) DDM(1.26) MMA (25) BL MAA (25) EA (50.74) CSEM25 (2.5) BX-AA (1) DDM (1.26)MMA (19.5)

After the preparation of the polymers, product emulsions are analyzed todetermine the pH, percent total solids (TS) based on polymer content,and Brookfield viscosity (spindle #2, 20 rpm, ambient room temperature).Additionally, the glass transition temperature (Tg) of selected productpolymers are determined by Method C above. The product polymeremulsions, as produced, generally have a pH of not more than about 5.5,typically in the range of about pH 2.5-4.5; total solids (TS) in therange of about 15 to about 45 weight percent; a Brookfield viscosity inthe range of about 10 to not more than about 100 mPa·s, and a Tg in therange of about 35° C. to about 150° C. The pH of the polymer emulsionscan be adjusted with acidic agents or alkaline agents to a pH preferablyin the range of about 3 to 7.5, or until the composition issubstantially clear or translucent, as desired. Where clarity is not aproblem or where alkaline pH is desired, the pH of the composition canbe adjusted to an alkaline pH of even greater than 12 and remain alkalistable as illustrated in the following examples.

EXAMPLES 2-8 Aqueous Gels

The aqueous gels were prepared by diluting the product polymer emulsionwith water to obtain the desired active polymer concentration and thenneutralizing the diluted polymer emulsion with2-amino-2-methyl-1-propanol (AMP, 95%) to a pH of about 5.8 to about7.5, or until the composition was substantially clear. The % clarityvalue was obtained by Method B, the viscosity was measured by Method A.The results obtained are set forth in Table 3.

These examples illustrate the rheology modification and clarity achievedin aqueous gels containing the inventive polymers. Comparative Examples2 and 3, illustrate the viscosity, and clarity of aqueous gelscontaining Comparative Polymer CP-1 of Example 1, a crosslinked,hydrophobically modified alkali-swellable emulsion (HASE) polymer havingone associative monomer, in the amounts shown in Table 3. Examples 4 to8 illustrate the thickening and clarity of aqueous gels containing,respectively, one the following inventive crosslinked ASAP from Example1, Polymer C, D, E, or F, in the amount indicated in Table 3, eachemploying one associative monomer (BEM25) that is the same associativemonomer of Comparative Polymer CP-1, and various different associativemonomers (i.e., a linear alkyl group (LEM23), complex ester (HCOEM25),or aryl-substituted alkyl group (TEM25)).

TABLE 3 Viscosity Viscosity Ex. Poly. Wt % mPa · s mPa · s No. No. Poly.pH % Clarity Immed. 24 hrs. 2 CP-1 1 7.4 67.5 14,300 18,400 3 CP-1 1.27.3 67.1 21,750 36,800 4 C 1 6.6 68.0 14,100 30,600 5 C 1.2 6.6 68.328,900 51,400 6 D 1.2 6.5 81.5 28,600 32,980 7 E 1.2 6.8 65.1 32,20057,400 8 F 1.2 6.5 69.5 29,200 56,400

As shown in Table 3 each of the aqueous compositions containing theinventive Polymers, C-F, achieved an initial gel viscosity substantiallysimilar to or greater than that of Comparative HASE Polymer CP-1 atcorresponding active polymer concentration of about 1 and about 1.2weight %. After 24 hours, the viscosity of all the gels of Polymers C-Fwas substantially greater than the gels of Comparative HASE Polymer CP-1at the corresponding concentration. Further, the aqueous gels made withthe inventive Polymers C-F achieved clarity at a lower pH (pH<7) thandid Comparative Polymer CP-1 (pH>7).

For further comparison, the gels of examples 2 and 3 were repeated,except that the Comparative HASE Polymer, CP-6, was employed. At anactive CP-6 polymer weight of about 1% and about pH 7.4, the 24-hourviscosity was 6,500 mPa·s and the % clarity was only about 26.2. At anactive CP-6 polymer weight of about 1.2% and about pH 6.7, the 24-hourviscosity was about 17,300 mPa·s and the % clarity was only about 29.9.

EXAMPLES 9-11 Aqueous Gels

Examples 9-11 respectively illustrate the viscosity and clarity achievedin aqueous gels containing the inventive Polymers A, K and L of Example1, each at active polymer concentrations of about 1.2 weight %, as shownin Table 4 below. Polymer A is a non-crosslinked analog of Polymer C ofExample 5. Polymers K and L illustrate crosslinked polymers havingdifferent crosslinkers and varying hydrophobe content. The gels wereprepared and neutralized to the pH indicated, and viscosity and %clarity determined as described in Examples 2-8.

TABLE 4 Viscosity Viscosity Ex. Poly. Wt % mPa · s mPa · s No. No. Poly.pH % Clarity Immed. 24 hrs 9 A 1.2 6.8 79.9 49,980 116,200 10 K 1.2 6.677.7 30,500 62,600 11 L 1.2 7.2 80.1 39,800 86,800

As shown in Table 4, the gel made with the inventive non-crosslinkedPolymer A (Ex. No. 9) had better clarity and higher viscosity than thegel containing non-crosslinked Polymer C of Example 5. The aqueous gelsmade with Polymers K and L (Ex. Nos. 10 and 11) also demonstrate goodthickening and clarity.

EXAMPLES 12-13 Aqueous Gels

Examples 12-13 illustrate the viscosity and clarity achieved in aqueousgels containing the inventive ASAP of Example 1, Polymer N (Ex. 12A,12B) and Polymer 0 (Ex. 13A, 13B), at the various active weight %indicated in Table 5. Polymer 0 has three different associativemonomers, two of which have linear alkyl hydrophobic end groups, and oneof which has a carbocyclic alkyl hydrophobic end group; whereas PolymerN has two associative monomers, one having a linear alkyl hydrophobicend group, and the other a carbocyclic alkyl hydrophobic end group. Theaqueous gels were prepared and neutralized to the pH indicated, andviscosity and % clarity determined as described in Examples 2-8.

TABLE 5 Viscosity Viscosity Ex. Poly. Wt % mPa · s mPa · s No. No.Polymer pH % Clarity Immed. 24 hrs. 12A N 1.5 6.5 79.9 23,450 32,400 12BN 2 6.3 79.2 34,350 51,600 13A O 1.5 6.6 54 66,800 85,800 13B O 2 6.552.2 122,800 164,800

Table 5 shows that, at the same active polymer concentration, theinventive Polymer O provided gels with greater viscosities than PolymerN.

EXAMPLES 14-15 Aqueous Gels

Examples 14-15 illustrate the viscosity and % clarity in aqueous hairsetting compositions containing 1.2 or 1.5 active weight % of ASAP,Polymer AB (Ex. 14A, 14B) or Polymer AM (Ex. 15A, 15B) of Example 1.Polymers AB and AM each have three different associative monomers, twoof which have linear alkyl hydrophobic end groups and one of which has acarbocyclic alkyl hydrophobic end group. The polymers have the same typeof semihydrophobic monomers and different types of crosslinkingmonomers.

The compositions were prepared employing the formulation shown in Table6.

TABLE 6 Ingredient Wt % Polymer, as indicated below 1-1.5 Propyleneglycol 0.5 Metal ion Chelating Agent 0.1 Preservative 0.5 AMP to pHindicated below q.s. Deionized Water to 100% q.s.

The viscosity was measured by Method A, and the % clarity was obtainedby Method B as shown below in Table 7.

TABLE 7 Polymer AB Polymer AM Ex. 14A Ex. 14B Ex. 15A Ex. 15B Polymer %(active) 1.2 1.5 1.2 1.5 pH 6.5 6.5 6.7 6.7 % Clarity 77.2 76.3 83.881.2 Viscosity (mPa · s) Immediate 4,740 13,460 21,150 39,550 24 hour7,400 16,650 30,800 39,800

Polymer AM provided a greater viscosity than Polymer AB. Both polymersprovided products having very good clarity.

EXAMPLES 16-28 Aqueous Gels

Examples 16-28 illustrate the clarity and viscosity achieved in aqueousgels containing the following ASAP of Example 1, crosslinked Polymers E(Exs. 16 A, B), F (Exs. 17A, B), H (Exs. 19A-C), J (Exs. 21A, B), K(Exs. 22 A, B), L, (Ex. 23A, B), M (Ex. 24 A-C) AT (Exs. 25 A-D), AU(Exs. 26 A-C), AV (Exs. 27A, B), AW (28 A, B) and non-crosslinkedPolymers G (Exs. 18 A-C) and I (Exs. 20 A, B) at various active weight %concentrations as indicated in Table 8 below. Crosslinked Polymers H andJ and non-crosslinked Polymers G and I contain chain transfer agents.Polymer M contains two crosslinking agents, one of which is ethoxylated.Polymers AT, AU, AV, and AW contain semihydrophobic monomer. The aqueousgels were prepared and neutralized to the pH indicated, and viscosityand % clarity determined as described in Examples 2-8. The results areshown in Table 8.

TABLE 8 Viscosity Viscosity Ex. Poly. Wt % % mPa · s mPa · s No. No.polymer pH Clarity Immed. 24 hr 16A E 1.5 6.8 65 73,200 109,800 16B E1.8 6.8 64.7 120,800 144,600 17A F 1.5 6.5 69.2 49,800 94,800 17B F 1.86.4 68.7 73,400 117,600 18A G 1.5 6.4 92.1 27,550 34,000 18B G 1.8 6.391.8 27,350 36,200 18C G 2 6.3 91 45,650 66,800 19A H 1.5 6.3 95.930,950 37,200 19B H 1.8 6.3 94.2 46,450 57,800 19C H 2 6.4 94 79,80086,600 20A I 1 6.4 96.5 23,800 35,050 20B I 1.2 6.2 95 42,600 79,200 21AJ 1 6.2 94.6 19,600 25,850 21B J 1.2 6.1 97 35,900 68,200 22A K 1.5 6.675.2 65,200 96,200 22B K 1.8 6.6 70.3 103,200 136,200 23A L 1.5 7 83.358,200 97,200 23B L 1.8 7.1 79.9 136,600 164,800 24A M 1.5 6.6 60.339,600 56,200 24B M 1.8 6.6 55.9 49,400 84,600 24C M 2 6.7 48.7 93,600119,400 25A AT 1 6.5 86.2 9,700 11,200 25B AT 1.2 6.5 84.3 13,850 14,00025C AT 1.5 6.5 82.5 36,200 44,400 25D AT 2 6.5 85.8 71,600 78,200 26A AU1 6.3 89.1 6,720 7,850 26B AU 1.2 6.3 87.2 8,100 9,300 26C AU 1.5 6.286.6 12,400 13,050 27A AV 1.5 6.5 92.3 — 23,200 27B AV 2 6.5 93.6 —50,000 28A AW 1.5 6.5 86.2 — 18,500 28B AW 2 6.5 87.6 — 32,700

The viscosities of all the aqueous gels containing Polymers E-M (Exs.16-24) underwent a substantial increase as these aqueous compositionsaged over 24 hours or so. Polymers G, H, I, J and K demonstrated asurprisingly enhanced clarity and viscosity, greater than even that ofPolymers E, F, L and M at similar concentration.

Surprisingly, the viscosity of Polymers AT-AU was substantiallyunchanged over 24 hours or so. Polymers AT-AW were judged suitable foreither high viscosity or gel compositions.

EXAMPLE 29 Aqueous Gels

This example demonstrates that ASAP can be combined withhydrophobically-modified carbomer polymer to provide gels (i.e., havinga Brookfield viscosity above 10,000 mPa·s) over a broad pH range ofabout 5.3 to about 13.3.

Nine aqueous gels (Exs. 29A-I) were separately prepared, eachcontaining, on a final weight basis, about 0.8 active weight % ASAP,Polymer AT of Ex. 1, and about 0.4 active weight %hydrophobically-modified carbomer polymer, CARBOPOL® Ultrez 21 polymer,(Noveon, Inc., Cleveland, Ohio), and each gel respectively havingsufficient neutralizing base (sodium hydroxide, 18%) to obtain a pH of5.3 (Ex. 29A), 7 (Ex. 29B), 8 (Ex. 29C), 9.1 (Ex. 29D), 10 (Ex. 29E),11.5 (Ex. 29F), 12.3 (Ex. 29G), 13.1 (Ex. 29H), and 13.3 (Ex. 291). Theviscosity of each gel was determined as described in Method A.Surprisingly, as shown by the following results, gels were obtained atall pH values: Brookfield viscosity in mPa·s was 49,800 (Ex. 29A);86,400 (Ex. 29B); 75,800 (Ex. 29C); 69,400 (Ex. 29D); 65,500 (Ex. 29E);63,700 (Ex. 29F); 57,600 (Ex. 29G); 32,100 (Ex. 29H); and 24,800 (Ex.291). Also demonstrated was that the two anionic polymers werecompatible over the entire pH range examined.

EXAMPLE 30 Aqueous Gels

Electrolytes are generally known to reduce the viscosity obtained withconventional carbomer polymer thickeners. This example demonstrates thatgenerally unexpectedly high viscosity surprisingly can be achieved withASAP, Polymer AT of Example 1, in the presence of an electrolyte (e.g.,sodium chloride), in combination with a hydrophobically modifiedcarbomer polymer, CARBOPOL® Ultrez 21 polymer, (Noveon, Inc., Cleveland,Ohio).

Gel Series A. An aqueous gel was prepared containing, on a total weightbasis, about 1.25 weight % Polymer AT of Example 1, neutralized with AMPto about pH 6.4-6.8. The gel had a Brookfield viscosity of about 22,400mPa·s. The procedure was repeated to provide three separate aqueousgels, except that each gel also contained, respectively, the followingweight % of sodium chloride, 0.1, 0.25, and 0.5. The salt decreased theBrookfield viscosity of the ASAP gel to about 8,100 mPa·s (0.1% salt),to about 3,200 mPa·s (0.25% salt) and to about 900 mPa·s (0.5% salt).

Gel Series B. The procedure of Series A was repeated, except that theaqueous gels contained, on a total weight basis, about 1.25 activeweight % CARBOPOL® Ultrez 21 polymer. The Brookfield viscosity of thesalt free gel was about 98,2001mPa·s, which was decreased by the salt toabout 61,800 mPa·s (0.1% salt), to about 44,600 mPa·s (0.25% salt), andto about 28,400 mPa·s (0.5% salt).

Gel Series C. The procedure of Series A was repeated, except that theaqueous gels contained, on a total weight basis, a total polymer weightof about 1.25 weight % comprised of about 0.75 active weight % PolymerAT and about 0.5 active weight % CARBOPOL® Ultrez 21 polymer. TheBrookfield viscosity of the salt free gel was about 105,000 mPa·s. TheBrookfield viscosity in the presence of salt remained unexpectedly highat about 71,200 mPa·s (0.1% salt), about 55,800 mPa·s (0.25% salt), andabout 42,050 mPa·s (0.5% salt).

The data surprisingly show that a combination of the ASAP andhydrophobically modified carbomer polymer provided gels having agenerally unexpectedly higher viscosity in the presence of electrolyte,as well as a generally higher salt tolerance than that of gelscontaining the individual polymer.

EXAMPLE 31 Sunscreen Lotions and Creams

This example illustrates the compatible use, on a total compositionweight basis, of a combination of ASAP, Polymer AT of Example 1, ateither about 0.5 active weight % (Ex. 31A) or about 1 active weight %(Ex. 31B) with about 0.15 active weight % carbomer polymer, CARBOPOL®980 polymer, (Noveon, Inc., Cleveland, Ohio), in a water-resistant typesunscreen formulation having a high SPF (Sun Protective Factor) value ofgreater than about 30.

In addition to the foregoing polymers, the sunscreen formulations of Ex.31A and 31B each also contained, on a total composition weight basis,about 2 active weight % hexylene glycol, about 7.5 active weight % octylmethoxycinnamate, about 6 active weight % benzophenone-3, about 5 activeweight % octyl salicylate, about 10 active weight % octylcrylene, about2 active weight % PEG-20 stearate (INCI name for CERASYNT 840, ISP VanDyk & Co., Belleville N.J.), about 5 weight % glycerylstearate(and)laureth-23 (INCI name for CERASYNT 945, ISP Van Dyk & Co.,Belleville N.J.), preservative (q.s.), deionized water (q.s. to 100weight %) and sufficient base (triethanolamine, 99%) to obtain a pH inthe range of about 6.5-6.6.

The Brookfield viscosity for Ex. 31A was about 19,400 in mPa·s and forEx. 31B was about 40,800 mPa·s. The viscosity remained substantiallyunchanged over a storage period of about two months at a temperature ofabout 45° C. The sunscreen of Ex. 31 A was an aesthetically smooth,glossy lotion and that of Ex. 31B was an aesthetically smooth, glossycream. Both sunscreens were judged as having excellent spreadability,and rich, firm, textural, sensory product attributes.

EXAMPLES 32-35 Skin Care Lotion

Examples 32-35 illustrate the stabilization of a skin care lotionformulation containing, on a total composition basis, about 0.25 activeweight % of the humectant salt, sodium PCA (INCI name for the sodiumsalt of DL-pyrrolidone carboxylic acid, sold under the trade nameAJIDEW® N-50, by Ajinomoto Inc., Teaneck, N.J.), employing relativelylow concentrations of ASAP, Polymer AT of Example 1, alone or incombination with hydrophobically-modified carbomer polymer, CARBOPOL®Ultrez 21 polymer, (Noveon, Inc., Cleveland, Ohio), while achieving highviscosity.

Five skin care lotions were separately prepared containing as thestabilizer, the following amounts, on a total composition weight basis:about 0.6 active weight % Polymer AT (Ex. 32A), about 1 active weight %Polymer AT (Ex. 32B); about 0.3 active weight % Polymer AT and about 0.3active weight % CARBOPOL® Ultrez 21 polymer (Ex. 33); about 0.6 weight %Polymer AT and about 0.3 active weight % CARBOPOL® Ultrez 21 polymer(Ex. 34); and about 0.6 active weight % of the carbomer polymer (Ex.35).

Each of the skin care lotions contained, in addition to the foregoingsodium PCA and polymer indicated, on a total composition weight basis,about 2 active weight % glycerin, about 3 active weight % sunflower seedoil, about 5 active weight % caprylic/capric triglycerides, about 4active weight % cetearyl octanoate, about 3 active weight % cocoabutter, preservative (q.s.), fragrance (q.s.), and sufficient AMP (95%)to obtain about pH 6.4-6.5.

The lotions of Exs. 32A, 32B, and 35 were prepared by generallyrecognized emulsion technique by combining the water insolublecomponents together to provide an oil phase, combining the glycerin,water, and polymer to provide a water phase, adding the oil phase to thewater phase, then adding the preservative and fragrance, and adjustingthe pH, as needed. The lotions of Exs. 33 and 34 were similarlyprepared, except that the polymers were blended by pre-dispersing theCARBOPOL® Ultrez 21 polymer in a portion of the water, then adding thePolymer AT was added to the dispersion, neutralizing the resultingpolymer blend, and then incorporating the resulting polymer blend intothe water phase.

All of the skin care lotions containing ASAP (Exs. 32A, 32B, 33 and 34)produced products having a Brookfield viscosity greater than 10,000mPa·s and remained physically stable, even after storage for a period ofat least two months at ambient room temperature and at elevatedtemperature (45° C.), with no loss in viscosity. In contrast, the lotionof Ex. 35 containing no ASAP was not stabilized (separated into twophases substantially immediately). All of the stabilized lotions of Exs.32-34 were judged aesthetically smooth, and easy to spread. The sensorytactile properties of the lotion of Ex. 34 were further enhanced byrepeating the preparation of the lotion and further including about 0.6active weight % of dimethicone PEG-7 isostearate (INCI name for awater-dispersible dimethicone copolyol ester sold under the trade name,ULTRASIL™ DW-18 silicone, by Noveon, Inc., Cleveland Ohio) without lossin stability, or viscosity under the foregoing storage temperatures andperiods.

EXAMPLE 36 Alkali-Soluble Associative Polymers

Alkali-soluble ASAP of the present invention, exemplified by Polymers BAthrough BL of Ex. 1, Table 2D, are judged useful in a variety ofapplications as foam enhancers, and as film formers in products whererelatively low thin viscosity is desired.

Aqueous solutions of Polymers BE, BF, BG, BI, BJ and BK, each of whichcontains one associative monomer, were prepared at active polymer weightconcentrations of about 3, 5, and 10%, and were neutralized to a pH inthe range of about 6.5 to about 7.5 with AMP (95%). At a polymerconcentration of about 3% by weight, the Brookfield viscosities of thesolutions were too low to measure. At about 5% by weight, each of thepolymers afforded a solution having a Brookfield viscosity of not morethan about 25 mPa·s. Even at about 10% concentration, the polymers allafforded aqueous solutions with Brookfield viscosities of not more thanabout 300 mPa·s.

The foregoing procedure was repeated, except that the aqueous solutionscontained Polymer BA, which has two associative monomers. The Brookfieldviscosity, at a Polymer BA concentration of about 3% was less than about15 mPa·s, of about 5%, was about 61 mPa·s, and of about 10% was about850 mPa·s.

In contrast, a 5% solution of a polymer similar to Polymers BI and BJ,but lacking the semihydrophobic monomer (i.e., a polymer comprising48.2% EA, 19.5% MMA, 29% MAA, 2.5% BEM25, and 0.8% DDM) had a Brookfieldviscosity of greater than about 3,000 mPa·s and an undesirable stringytexture. Similarly, a 5% solution of another similar polymer havingneither a semihydrophobic monomer nor a chain transfer agent (i.e., apolymer comprising 49% EA, 19.5% MMA, 29% MAA and 2.5% BEM25) had aBrookfield viscosity of greater than about 300,000 mPa·s and anundesirable lumpy texture.

The alkali-soluble associative polymers of the present invention arejudged as excellent foam enhancers for aqueous and hydro-alcoholic pumpand spray foam products, such as shaving creams, foaming hair fixatives,foam-type cleansing agents, and the like. The polymers are compatibleand soluble in aqueous alcohol solutions containing up to at least about55% by volume ethanol, at polymer concentrations of at least about 5% byweight making them suitable for low VOC (not more than about 55%volatile organic compounds) compositions.

The alkali-soluble associative polymers of the present invention arealso compatible with hydrocarbons, making the polymers useful in highVOC pressurized or non-pressurized aerosol spray applications (up to atleast about 85% VOC) as well. For example, in a solution of about 20% byvolume cyclohexane in ethanol (95%) the solubility of Polymer BJ of Ex.1 was about 5 active weight % at room temperature and about 2 activeweight % at a temperature of about 4° C. In a solution of 50% by volumecyclohexane in ethanol (95%), Polymer BJ was soluble at a concentrationof about 1 active weight % at both room temperature and at about 4° C.The solutions remained clear and transparent (i.e., no cloudiness wasobserved).

Polymers BG and BI were each separately formulated in 55% aqueousethanol at a level of about 5 active weight % polymer and neutralizedwith AMP (95%) to a pH in the range of about 7 to about 8. Each ASAPprovided a solution having a Brookfield viscosity of about 5 mPa·s.Polymer BG provided a fine mist spray when pumped from a manuallyactuated pump sprayer. Polymer BI afforded a rich, thick, glossy foamwhen dispensed from a mechanical, non-pressurized aerosol foam dispenser(e.g., mechanical foam dispensers available from Airspray International,Inc., Pompano Beach, Fla.). Both formulations provided excellent highhumidity resistance, based on Method F when applied to hair, did notleave a flaky residue on the hair and washed out easily.

The alkali-soluble ASAP are judged suitable for use in hydrocarbon-based(e.g., n-butane, pentane, and isobutane) pressurized aerosolformulations and for non-pressurized aerosol formulations where nochemical or gaseous propellants are used.

EXAMPLE 37 Humidity Resistance

The humidity resistance of the hair tresses treated by the inventivepolymers was assessed by the procedure of Method F, based on an HHCR ofa minimum of 70% Curl Retention on hair. The aqueous gel compositionscontaining Polymers C, D, E and F of Examples 4-8 and 16-19, Polymers A,K and L of Examples 9-11, Polymers N and O of Examples 12-13, PolymersG-M and AT-AW of Examples 18-28 were evaluated. Surprisingly, all of theinventive polymers demonstrated very good to excellent high humidityresistance, i.e., an HHCR of at least 70% or more curl retention for aminimum of about four hours. The subjective curl memory(bouncy/restylability) properties of the curled hair assessed by MethodG above were also judged good to excellent after exposure to 90% RH over24 hours indicating that the inventive associative polymers weresuitable for use in hair care applications for hair setting and styling.

EXAMPLES 38-40 Aqueous Formulations

The procedure of Examples 14-15 was followed except that the inventiveASAP of Example 1, Polymers P (Ex 38A, 38B, 38C), Q (Ex. 39A, 39B, 39C),and R (Ex. 40A, 40B, 40C) were employed in the amounts shown in Table 7.Each of Polymers P, Q, and R has the same type of associative monomerand crosslinker; and Polymers Q and R also contain differentsemihydrophobic monomers.

Additionally, the gel texture was assessed by spreading a portion of thegel or viscous formulation over a MYLAR® film substrate employing a 10mil opening draw down applicator and observing its smoothness andspreadability characteristic. When the texture of the gel coating wassmooth and spreadable, it was rated as “S”; when the gel coatingappeared grainy, it was rated as “G”. The results are shown in Table 9below.

TABLE 9 Visc. Visc. Ex. Poly. Wt % % mPa · s mPa · s Gel No. No. Poly.pH Clarity Immed. 24 hrs. Texture 38A P 1 6.8 88.2 13,500 14,800 S 38B P1.2 6.8 84.6 24,500 26,750 S 38C P 1.5 6.8 81.7 39,750 42,500 G 39A Q 16.8 71.8 8,800 9,200 S 39B Q 1.2 6.8 63.6 13,750 13,500 S 39C Q 1.5 6.965 26,250 27,000 S 40A R 1 6.9 94.9 9,500 10,000 S 40B R 1.2 6.9 92.819,500 19,500 S 40C R 1.5 6.8 93.8 27,250 29,000 S

As shown in Table 9, all the polymers produced “S” gel textures, exceptfor the crosslinked Polymer P at a concentration of 1.5% (Ex. 38C). Thetexture of the gels obtained with Polymers Q and R were judged to besoft, smooth, and spreadable, even as the concentration of the polymerincreased, compared to the texture of the gels obtained with Polymer P,containing no semihydrophobic monomer. Additionally, Polymers Q and Rproduced gels having a viscosity that remained substantially unchangedover a 24-hour period.

Surprisingly, at all concentrations, Polymers P, Q and R demonstratedgood to excellent high humidity resistance, based on an HHCR of greaterthan 70% curl retention by Method F over a period of about four hoursexposure.

EXAMPLE 41-44 Aqueous Formulations

In Examples 41-44, the procedure of Examples 38-40 was followed exceptthat the inventive ASAP of Example 1, Polymers AF (Ex. 41A, B), AG (Ex.42A, B), AH (Ex. 43A, B), and AI (Ex. 44A, B), were employed at theamounts shown in Table 10. The polymers have varying amounts of the sametype of semihydrophobic monomer.

The aqueous gels were prepared and neutralized to the pH indicated inTable 10 below as described in Examples 2-8. The texture of the gels wasevaluated as described in Examples 38-40. The results are in Table 10.

TABLE 10 Visc. Visc. Ex. Poly. Wt % % mPa · s mPa · s Gel No. No. Poly.pH Clarity Immed. 24 hrs. Texture 41A AF 1 7 83.6 18,600 26,650 S 41B AF1.2 6.9 82.9 23,650 34,900 S 42A AG 1 6.9 67 13,550 18,350 S 42B AG 1.26.9 65.8 21,050 32,400 S 43A AH 1 7 85.5 16,700 25,450 S 43B AH 1.2 6.986.4 22,950 36,400 S 44A AI 1 6.7 93.6 16,550 23,500 S 44B AI 1.2 6.692.8 21,700 28,800 S

The data show that at all concentrations, the texture of the gelproduced was smooth and spreadable (“S”). Each of the polymer gels wasalso found to have excellent high humidity resistance, based on an HHCRof greater than 70% curl retention by Method F over a period of morethan four hours exposure. Surprisingly, varying the amount ofsemihydrophobic monomer from about 2.5 weight % (Polymer AF) up to about15 weight % (Polymer AI) had no adverse effect on the viscosity of thegels at each concentration.

EXAMPLES 45-50 Aqueous Gels

The procedure of Examples 14-15 was followed, except that the ASAP ofExample 1, Polymer X (Ex. 45A, 45B, 45C), Polymer Y (Ex. 46A, 46B, 46C),Polymer Z (Ex. 47A, 47B, 47C), Polymer AO (Ex. 48A, 48B), Polymer AP(Ex. 49A, 49B), and Polymer AQ (Ex. 50A, 50B), were employed in theamounts shown in Table 11. Each polymer contains a semihydrophobicmonomer component and two associative monomer components; and PolymersAO and AP each also have two nonionic vinyl monomer components.

The % clarity and viscosity at various active weight % polymer asindicated are shown in Table 11.

TABLE 11 Visc. Visc. Ex. Poly. Wt % % mPa · s mPa · s No. No. Poly. pHClarity Immed. 24 hrs. 45A X 1 6.9 90.4 11,600 12,800 45B X 1.2 6.9 90.920,000 20,500 45C X 1.5 6.8 88.1 38,750 38,250 46A Y 1 6.8 81.4 12,80014,100 46B Y 1.2 6.9 83.3 24,750 28,500 46C Y 1.5 6.8 86.3 59,000 63,00047A Z 1 6.8 79 7,700 7,760 47B Z 1.2 6.9 78.5 15,500 14,960 47C Z 1.56.8 78 27,500 31,350 48A AO 1 6.4 80.2 8,230 11,650 48B AO 1.5 6.8 81.722,790 37,850 49A AP 1 6.9 89.2 9,780 14,890 49B AP 1.5 6.9 88.7 20,96038,970 50A AQ 1 7 78.1 9,440 13,990 50B AQ 1.5 7.2 78 27,940 47,700

The data show that each of the Polymers demonstrated good clarity andviscosity. The high humidity resistance of each of the polymers was alsojudged excellent, based on 70% curl retention for more than four hoursexposure.

EXAMPLE 51 Aqueous Silicone Gels

This example illustrates aqueous silicone-containing gels preparedemploying ASAP of Example 1, Polymer K (Ex. 51A) and Polymer M (Ex.51B), in the amounts and composition shown in Table 12.

TABLE 12 Ex. 51A Ex. 51B Ingredients Weight % Weight % Polymer 1 1.5 AMP(95%) To pH 7.4 To pH 6.4 Dimethicone PEG-7 1.5 1 phthalate (Note 1)Preservative q.s q.s Fragrance q.s. q.s. Deionized water q.s. q.s. to100% Viscosity (24 hrs.) 33,000 39,200 q.s. = Quantity sufficient tomeet the requirement (Note 1) INCI name for a water-soluble, anionicsilicone carboxy compound sold under the trade name ULTRASIL ™ CA-1, byNoveon, Inc.

EXAMPLE 52 Hydro-Alcoholic Spray

Example 52 illustrates the use of about 1.5 (Ex. 52A) and about 2 (Ex.52B) active weight % of Polymer M of Example 1 in a spray compositionhaving a low volatile organic compounds (VOC) content employing ahydro-alcoholic solvent system comprising 55% ethanol and water,neutralizing anine (AMP), preservative and fragrance as shown in Table13.

TABLE 13 Ex. 52A Ex. 52B Ingredients Weight % Weight % Polymer M 1.5 2Ethanol, SD 40 55 55 AMP (95%) To pH 6.9 To pH 6.7 Preservative q.s.q.s. Deionized water to 100% q.s. q.s. Fragrance q.s. q.s.

The formulations showed a good, substantially uniform spray pattern whendispensed from a manually actuated pump spray and were suitable for usein low VOC sprays, such as those desired for hair care applications.

EXAMPLE 53 Facial Scrub

Example 53 illustrates the clarity, thickening and suspension efficacyof inventive Polymer A of Example 1 (Ex. 53A) and a non-crosslinkedComparative HASE Polymer, CP-2 (Ex. 53B), in the following highsurfactant, low pH formulation shown in Table 14 at an active polymerweight of about 1.5% suitable as a facial scrub.

TABLE 14 Ingredients (INCI/Trade Name) Wt. % 1. Polymer as indicatedbelow in Table 15 1.5 2. Sodium C₁₄-C₁₆ Olefin sulfonate (40%) 45 (Note2) 3. NaOH (18%) To pH 6.5 q.s. 4. Glycerin 2 5. Salicylic acid (USP) 26. Jojoba esters (Note 3) 2 7. Cocamidopropyl betaine (35%) 10 8.Fragrance q.s. 9. FD&C Red 33 (0.1%) 0.1 10. D&C Yellow # 6 (0.1%) 0.211. Citric acid (50%) To pH 5.2-5.4 q.s. 12. Deionized water To 100%q.s. (Note 2) Alpha olefin sulfonate, such as BIO-TERGE ® AS-40, StepanCompany. (Note 3) INCI name for microspheres of jojoba esters, such asFLORABEADS ® sold by International Flora Technologies, Ltd.

The composition was prepared by pre-gelling ingredient #1 by dispersingit in a portion of the water (#12), admixing therein a portion of theprimary surfactant, ingredient #2, with mild stirring to avoid aeration,and neutralizing the polymer admixture with ingredient #3 to about pH6.5 and then adjusting the pH of the resulting gel to about pH 5.2-5.4with ingredient #11 to provide a gel phase. Separately, ingredients #4,5 and the remaining portions of the water (#12) and primary surfactant(#2) were admixed to dissolve and the resulting solution was addedslowly with mild mixing agitation to the gel phase. The secondarysurfactant, ingredient #7, and remaining ingredients (#6, 8, 9 and 10)were then added, taking care to avoid aerating agitation. The turbiditywas determined before adding the product colorants. The final pH andviscosity was measured after 24 hours aging at ambient room temperature(about 25° C.). The results are shown in Table 15.

TABLE 15 Ex. 53B Ex. 53A (Comparative (Polymer A) Polymer CP-2) Final pH4 4 Viscosity (#6 @ 20 rpm), 14,600 11,500 mPa · s Turbidity NTU (Beforecolor) 41.5 128

The composition containing Polymer A (Ex. 53A) had good clarity whereasthe composition containing Comparative Polymer CP-2 (Ex. 53B) wasturbid. Suspension of the jojoba beads was visually assessed after 12weeks accelerated storage aging in an oven at about 45° C. Both polymersmaintained a stable suspension of the jojoba ester beads duringaccelerated aging.

EXAMPLE 54 Surfactant Cleansers

This example illustrates the clarity, viscosity and suspendingproperties of ASAP of Example 1, Polymer M (Ex. 54A), Polymer U (Ex.54B), Polymer AK (Ex. 54C), and Polymer D (Ex. 54D) and that ofcomparative polymer, CP-6, of Example 1 (Ex. 54E), each at an activepolymer concentration of about 2 weight % employing the formulationprovided in Table 16, suitable for use as a body wash, skin cleanser orshampoo.

TABLE 16 Ingredients (INCI/Trade Name) Wt % 1. Polymer, as indicatedbelow in Table 17 2 2. Sodium laureth sulfate (28%) (Note 4) 30 3. NaOH(18%) to pH indicated q.s. 4. Propylene glycol 2 5. Cocamidopropylbetaine (35%) 4 6. EDTA, Disodium 0.1 7. Preservative q.s. 8. U.V.Absorber q.s. 9. Fragrance solubilized in Polysorbate-20 q.s. 10. FD&CBlue #1 (0.1%) 0.05 11. D&C Yellow #10 (0.1%) 1.5 12. Vitamin E (and)Gelatin beads (Note 5) 1 13. Deionized water To 100% q.s. (Note 4)Ethoxylated with 3 moles ethylene oxide, such as STANDAPOL ® ES-3,Cognis Corporation. (Note 5) INCI name for product sold under thetrademark, LIPOPEARLS ®, Lipo Chemicals, Inc.

The compositions were prepared by pre-gelling ingredient #1 bydispersing it in a portion of the water (#13), admixing the primarysurfactant, ingredient #2, therein with gentle stirring agitation toavoid foaming, neutralizing the polymer mixture to about pH 6.7 withingredient #3, and adding ingredient #4 to the neutralized polymermixture to provide a gel phase. Separately, ingredients #6 and 8 werepremixed with the remaining portion of the water (#13), heating todissolve and then adding the resultant solution to the gel phase. Thesecondary surfactant, ingredient #5, was then added to the resultingmixture with gentle stirring agitation, followed by addition of theremaining ingredients, #9, 7, 12, 10 and 11 and the final pH adjustedwith ingredient #3, if necessary.

The % clarity was evaluated by Method B before adding the productcolorants. After 24 hours and after accelerated aging of the products inan oven at about 45° C. for up to about 12 weeks, the pH and viscositywere again determined. The results are shown in Table 17.

TABLE 17 Ex. 54A Ex. 54B Ex. 54C Ex. 54D Ex. 54E Polymer Polymer PolymerPolymer Polymer M U AK D CP-6 pH 6.7 6.6 6.6 6.6 6.5 Visc. (#4@20 rpm),1,660 1,800 7,300 8,400 456 mPa · s % Clarity 86.4 85.7 — — 25.2 (Beforecolor) Storage Stability 12 12 10 8 — @ 45° C. Weeks Weeks Weeks WeekspH 6.51 6.5 — — — Visc. (#4@20 rpm), 2,900 3,330 10,280 7,000 — mPa · s

The suspension of the water-insoluble beads (ingredient #12) wasvisually assessed. Initially only a few beads settled during theformation of the composition or over a 24-hour period. Duringaccelerated aging storage at about 45° C., the beads remainedsubstantially suspended (slight settling) for a period of about 12 weeksin the compositions containing Polymer M (Ex. 54A) and Polymer U (Ex.54B). The suspension of the beads was also judged substantially stablefor a period of about eight weeks in the composition containing PolymerAK (Ex. 54C) and for a period of about four weeks in the compositioncontaining Polymer D (Ex. 54D).

In contrast, the beads were not suspended by the Comparative PolymerCP-6 (Ex. 54E) and settled out of the composition in less than 24 hours.

EXAMPLE 55 Emulsions

This example illustrates the use of about 1% active polymer weight ASAPof Example 1, Polymer N (Ex. 55A) and Polymer M (Ex. 55B), each inoil-in-water emulsions suitable for use as hand and body lotions orcreams, as shown in Table 18.

TABLE 18 Ex. 55A Ex. 55B Ingredients (INCI/Trade Name) Weight % Weight %Mineral oil 8 8 Octyl stearate 4.5 4.5 Lanolin 0.5 0.5 Cetyl alcohol 1.51.5 Glyceryl stearate 5 5 Dimethicone 0.1 0.1 Polymer 1 1 Deionizedwater to 100% q.s. q.s. NaOH, 10% To pH 6.1 To pH 6.5 Glycerin — 3Propylene glycol 2 2 Preservative 0.5 0.5 Fragrance q.s. q.s. Viscosity,mPa · s 20,050 14,800 Appearance at RT glossy, white glossy, whitelotion lotion Feel on skin Non-tacky & Non-tacky & smooth feel smoothfeel Viscosity, mPa · s after Aging for 14 Weeks Room Temperature (about25° C.) — 18,200 35° C. — 16,400 50° C. — 12,600 Appearance afteraccelerated storage smooth smooth

EXAMPLE 56 Liquid Surfactant

This example illustrates the use of Polymer A of Example 1 (Ex. 56A),which contains two associative monomers, and Comparative HASE PolymerCP-2 of Example 1 (Ex. 56B), which contains one associative monomer,each at an active polymer weight of about 1.5%, employed in a liquidsurfactant suitable for use as a hand dishwashing liquid having theformulation shown in Table 19.

TABLE 19 Ingredient Wt % Polymer, as indicated below in Table 20 1.5Ammonium lauryl sulfate (30%) 25 Sodium laureth sulfate (30%) (Note 4,Table 16) 25 Sodium citrate 0.5 Sodium hydroxide (18%) to pH 6.5-7 q.s.Deionized Water to 100% q.s.

The composition can be prepared by adding the surfactants to an aqueoussolution of the polymer with slow mixing agitation to avoid excessivefoam generation, adding the sodium citrate to dissolve, and adjustingthe pH with sodium hydroxide. If desired, fragrance and product colorantalso can be added. The viscosity and turbidity at about pH 6.5-7 areshown in Table 20.

TABLE 20 Ex. 56B Ex. 56A Comparative Polymer A Polymer CP-2 ViscositymPa · s 16,600 21,000 Turbidity NTU 20.3 108.3

Polymer A (Ex. 56A) produced a substantially clear composition whereasthe Comparative HASE Polymer CP-2 (Ex. 56B) produced a turbidcomposition.

The foregoing formulations were each further acidified with citric acidto about pH 5 to provide a lower viscosity product. The viscosity andturbidity at about pH 5 are shown in Table 21.

TABLE 21 Ex. 56B-pH 5 Ex. 56A-pH 5 Comparative Polymer A Polymer CP-2Viscosity mPa · s 5,700 4,200 Turbidity NTU 34.9 90

Again, Polymer A (Ex. 56A-pH 5) produced a significantly clearer productthan did Comparative HASE Polymer CP-2 (Ex. 56B-pH 5).

EXAMPLE 57 Hydro-Alcoholic Gels

This example illustrates the use of an active polymer weight of about1.5% Polymer L in a hydro-alcoholic gel formulation containing camphor.The formulation shown in Table 22 had a pH of about 7.3 and a viscosityof about 5,140 mPa·s.

TABLE 22 Ingredient Weight % Polymer L 1.5 EDTA, Disodium 0.1 Isopropylalcohol 10 Camphor (crystals) 0.2 Polysorbate 20 1 Triethanolamine (TEA,99%) to pH 7.3 q.s. Preservative 0.2 FD&C Blue No. 1 (5%) to color q.s.Deionized water to 100% q.s.

Another series of hydro-alcoholic gel embodiments were preparedcontaining Polymer G, H, I, or J of Example 1 at an active polymerweight % of about 3.5-4%, about 10-30% ethanol, and relatively low totalamounts (<0.2%) of hair conditioning agents (Panthenol, dimethiconecopolyol), preservative, solubilized fragrance and product colorant,neutralized with TEA to a pH of about 6-6.5. These hydro-alcoholiccompositions had a viscosity in the range of about 7,500 mPa·s to about90,000 mPa·s. The specular gloss produced by these compositions wasdetermined by Method D. At an angle of 20°, the gloss value units werein the range of about 40 to about 60 and at an angle of 60°, the glossvalue units were in the range of about 85 to about 90. Thesecompositions were judged suitable for personal care and household careapplications.

EXAMPLE 58 Highly Alkaline Washing Gels

This example illustrates the use of Polymer AE and of Comparative HASEPolymer CP-3 in a highly alkaline (pH>12.5) formulation containingdisinfectant, suitable for use as automatic dishwashing liquids, surfacecleaners and the like, employing the formulation shown in Table 23. Theresults are shown in Table 24.

TABLE 23 Ingredient Weight % Polymer, as indicated below in Table 24 1Deionized Water to 100% q.s. Rheology stabilizer(Note 6) 0.1 Potassiumcarbonate 5 Potassium silicate (39%) 15 Potassium hydroxide (45%) 5Sodium hydroxide (50%) 5 Sodium tripolyphosphate 20 Sodium xylenesulfonate (40%) 0.5 Sodium hypochlorite (12.5% Available Chlorine) 8(Note 6): OXY-RITE ®, Noveon, Inc. (Example suitable rheologystabilizers are described in U.S. Pat. No. 6,083,422 to Ambuter et al,incorporated herein by reference.)

TABLE 24 Viscosity mPa · s at about 25° C. Polymer No. Immed. 24 Hr. 1Week AE, Ex. 1 350 1,020 36,000 CP-3, Ex. 1 350 1,120 19,500

The stability of the viscosity was judged acceptable in the art.

If higher or lower viscosity is desired, the active weight % of thepolymer can be increased or decreased accordingly.

If desired, an oxygen releasing disinfectant, such as a hydrogenperoxide compound, may be substituted in place of the chlorine bleach.

EXAMPLE 59 Highly Alkaline Washing Liquids

This example illustrates the use of Polymer AE and of Comparative HASEPolymer CP-3 in a highly alkaline (pH>12.5) formulation containingdisinfectant, suitable for use as substantially clear, bleach-containinglaundry prespotters, bleach-containing mold and mildew cleansers, andthe like, employing the formulation shown in Table 25. The results areshown in Table 26.

TABLE 25 Ingredient Weight % Polymer, as indicated in Table 26 1Deionized Water to 100% q.s. Rheology stabilizer (Note 6, Table 23) 0.1Sodium hydroxide (50%) 2.5 Sodium hypochlorite (12.5% AvailableChlorine) 8

TABLE 26 Viscosity mPa · s at 25° C. at 45° C. Polymer No. Immed. 4weeks 4 weeks AE, Ex. 1 2,900 6,300 5,200 CP-3, Ex. 1 2,200 5,750 6,100

The products were prepared by combining the polymer, water and rheologystabilizer, adjusting the pH with the sodium hydroxide to greater thanabout pH 12.5, and then adding the chlorine bleach. Fragrance can beadded, if desired. Alternatively, an oxygen releasing bleach, such as ahydrogen peroxide compound, may be substituted in place of the chlorinebleach.

EXAMPLE 60 Aqueous Silicone Gels

This example illustrates the use of ASAP of Example 1, Polymers Q (Ex.60A), Y (Ex. 60B) and Z (Ex. 60C) each in aqueous siliconepolymer-containing gels employing an active polymer weight of about 1.5%in the formulation shown in Table 27. The results are shown in Table 28.

TABLE 27 Ingredient Weight % Polymer, as indicated in Table 28 1.5Deionized Water to 100% q.s. Solubilized fragrance q.s. DimethiconePEG-7 phthalate (Note 1, Table 12) 0.3 UV Stabilizer q.s. Preservativeq.s. AMP to pH as indicated in Table 28 q.s.

TABLE 28 Ex. 60A Ex. 60B Ex. 60C (Polymer Q) (Polymer Y) (Polymer Z) pH6.9 7.1 7 Immed. Visc., mPa · s 59,800 77,800 58,000 24 Hr. Visc., mPa ·s 60,200 77,900 58,200 % Clarity 62.9 76.2 75.4

EXAMPLE 61 Aqueous Conditioning Gels

This example illustrates the use of ASAP of Example 1, Polymers Q (Ex.61A), Y (Ex. 61B) and Z (Ex. 61C), each at an active polymer weight ofabout 1.2% in aqueous gels containing a cationic conditioning agentemploying the formulation shown in Table 29. The results are in Table30.

TABLE 29 Ingredient Weight % Polymer, as indicated in Table 30 1.2Deionized Water to 100% q.s. Panthenol 0.1 Solubilized fragrance q.s.Polyquaternium-11 (Note 7) 0.1 Preservative q.s AMP to pH indicated inTable 30 q.s. (Note 7) INCI name for quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, neutralized(GAFQUAT ® 755N, ISP).

TABLE 30 Ex. 61A Ex. 61B Ex. 61C (Polymer Q) (Polymer Y) (Polymer Z) pH7.1 7.1 7.1 Immed. Visc., mPa · s 41,200 37,800 48,200 24 Hr. Visc., mPa· s 38,100 38,400 79,000 % Clarity 60.5 72 71.8

EXAMPLE 62 Clear Spray Gels

This example illustrates the use of ASAP of Example 1, Polymers A (Ex.62A), C (Ex. 62B), and Y (Ex. 62C), each an active polymer weight ofabout 0.8% in aqueous clear spray gels employing the formulation shownin Table 31. The results are shown in Table 32.

TABLE 31 Ingredient Weight % Polymer, as indicated in Table 32 0.8Deionized Water to 100% q.s. Glycerin 2   Preservative q.s.Triethanolamine to pH indicated in Table 32 q.s. Metal ion chelatingagent q.s.

TABLE 32 Ex. 62A Ex. 62B Ex. 62C (Polymer A) (Polymer C) (Polymer Y) pH6.8 7 6.5 Immed. Visc., mPa · s 7,520 7,800 2,940 24 Hr. Visc., mPa · s9,440 8,040 4,600 % Clarity 73 69 82

EXAMPLE 63 Textile Treatments

This example illustrates the use of Polymer AS as a thickener in atextile print paste (Ex. 63A) and in a textile coating formulation (Ex.63B), at the active polymer weight % indicated in Table 33.

TABLE 33 Weight % Ingredient Ex. 63A Ex. 63B Water to 100% q.s. q.s.Polymer AS, Ex. 1 1.5     0.76 Ammonium hydroxide (28%) to pH 9.7    8.5 Acrylic emulsion binder 5 (Note 8) 41.86 (Note 9) Pigment 5 —General defoamer (Note 10) —     0.25 Ammonium nitrate (25%) —     0.45Viscosity, mPa · s (24 hours) 28,000 244,500* *Brookfield Model RVF,Spindle #6 at 4 rpm. (Note 8) PRINTRITE ® 595, Noveon, Inc. (Note 9)HYCAR ® 2671, Noveon, Inc. (Note 10) FOAMASTER ® DF-160L, Henkel Corp.

EXAMPLE 64 Conditioning Shampoo

This example illustrates the use of Polymer U of Example 1 in apearlescent conditioning shampoo at an active polymer weight of about1.5% employing the formulation shown in Table 34.

TABLE 34 Ingredients (INCI/Trade Name) Wt. % Part A  1. Deionized water40.3  2. Polymer U, Ex. 1 1.5  3. Sodium laureth sulfate (28%) (Note 4,Table 16) 30  4. NaOH (18%) to pH 6.5 q.s. Part B  5. Cocoamidopropylhydroxysultaine (50%) 10  6. Disodium laureth sulfosuccinate (40%) 10Part C  7. Deionized water 3  8. Mica and titanium dioxide (Note 11) 0.2Part D  9. Dimethicone (60,000 cst) (Note 12) 3 10. Preservative q.s.   Fragrance q.s. 11. Citric Acid (50%) to pH 5.3-5.7 q.s. final weight 100(Note 11) Mixture sold under the trade name TIMIRON ® MP-115 Starlusterby Rona/Merck KGaA. (Note 12) A volatile dimethyl polysiloxane soldunder the trade name Dow Corning 200 Fluid by Dow Corning Corporation.

Part A of the shampoo was prepared by admixing Polymer U and deionizedwater, then mixing in the surfactant (#3) with gentle mixing action andthen adjusting the mixture to a pH of about 6.5 with the alkali (#4) toprovide a gel phase. The ingredients of Part B were then admixed intothe gel phase in the order listed. The ingredients of Part C werepremixed and the premix was added to the foregoing batch mixture.Ingredients #9 and #10 of Part D were then added to the batch in theorder listed and the pH of the final shampoo was adjusted withingredient #11.

The final pH of the pearlescent shampoo product was about pH 5.5, theBrookfield viscosity was about 3,640 mPa·s initially and about 4,420mPa·s after 24 hours. The pearlescent shampoo can also be prepared withmica or titanium dioxide as the opacifying, cosmetic pigment, ingredient#8.

EXAMPLES 65-69 Aqueous Gels

It is known that the viscosity achieved with commonly employed anionicpolymeric thickeners can be negatively affected by the presence of someconventional anionic polymers. This example illustrates thecompatibility of the ASAP of this invention with anionic polymericthickeners, such as carbomer polymer, and hydrophobically-modifiedcarbomer polymer, in aqueous gels.

A first series of aqueous gels (Exs. 65-69) were separately prepared,each gel containing one of the following ASAP of Example 1: Polymer H(Exs. 65 A-I), Polymer Y (Exs. 66 A-I), Polymer Z (Exs. 67 A-I), PolymerAT (Exs. 68 A-L), Polymer AU (Exs. 69 A-I) and either a carbomerpolymer, or hydrophobically-modified carbomer, as identified, and in theamount indicated, in Tables 35-39, respectively. The commercialthickener products employed having the INCI name, Carbomer, were: atraditional carbomer polymer, CARBOPOL® 980 polymer, and ahydrophobically-modified carbomer polymer, CARBOPOL® Ultrez 21 polymer,both sold by Noveon, Inc. (Cleveland, Ohio). Other commercialhydrophobically-modified carbomer polymers employed were: CARBOPOL® ETD2020 polymer, also sold by Noveon, Inc., having the INCI name,Acrylates/C₁₀₋₃₀ Alkyl Acrylate Crosspolymer, and STABYLEN® 30, sold by3V Inc., having the INCI name, Acrylates/Vinyl Isodecanoate.

The aqueous gels were prepared by dispersing the selected commercialpolymeric thickener in a portion of the total water content,neutralizing the dispersion with AMP (95%) to a pH in the range of about6-6.5, then adding the required selected amount of aqueous emulsion ofASAP of Example 1, and adjusting the water content and pH, if needed, tomaintain the foregoing pH or clarity. The pH, % clarity, and viscosity(24-hour) of the gels is shown in Tables 35-39.

TABLE 35 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. % pHClarity (24 hours) 65A Polymer H, Ex. 1 0.5 6.4 90.2 47,600 CARBOPOL ®ETD 0.5 2020 65B Polymer H, Ex. 1 0.75 6.2 84.4 64,200 CARBOPOL ® ETD0.5 2020 65C Polymer H, Ex. 1 1 6.4 89.6 65,800 CARBOPOL ® ETD 0.25 202065D Polymer H, Ex. 1 0.5 6.4 92.8 42,800 CARBOPOL ® 980 0.5 65E PolymerH, Ex. 1 0.75 6.4 90.2 52,000 CARBOPOL ® 980 0.5 65F Polymer H, Ex. 1 16.5 90.9 49,200 CARBOPOL ® 980 0.25 65G Polymer H, Ex. 1 0.5 6.4 93.772,200 CARBOPOL ® Ultrez 21 0.5 65H Polymer H, Ex. 1 0.75 6.4 92.888,200 CARBOPOL ® Ultrez 21 0.5 65I Polymer H, Ex. 1 1 6.4 93.2 76,600CARBOPOL ® Ultrez 21 0.25

TABLE 36 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. % pHClarity (24 hours) 66A Polymer Y, Ex. 1 0.5 6.4 82.6 44,600 CARBOPOL ®ETD 2020 0.5 66B Polymer Y, Ex. 1 0.75 6.3 79.8 57,800 CARBOPOL ® ETD2020 0.5 66C Polymer Y, Ex. 1 1 6.4 78.3 55,800 CARBOPOL ® ETD 2020 0.2566D Polymer Y, Ex. 1 0.5 6.4 88.1 44,700 CARBOPOL ® 980 0.5 66E PolymerY, Ex. 1 0.75 6.4 84.5 55,200 CARBOPOL ® 980 0.5 66F Polymer Y, Ex. 1 16.4 88 50,000 CARBOPOL ® 980 0.25 66G Polymer Y, Ex. 1 0.5 6.5 91.963,600 CARBOPOL ® Ultrez 21 0.5 66H Polymer Y, Ex. 1 0.75 6.5 92 81,800CARBOPOL ® Ultrez 21 0.5 66I Polymer Y, Ex. 1 1 6.5 91.3 59,800CARBOPOL ® Ultrez 21 0.25

TABLE 37 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. % pHClarity (24 hours) 67A Polymer Z, Ex. 1 0.5 6.3 76.9 40,200 CARBOPOL ®ETD 2020 0.5 67B Polymer Z, Ex. 1 0.75 6.5 81.2 57,200 CARBOPOL ® ETD2020 0.5 67C Polymer Z, Ex. 1 1 6.4 80.9 36,200 CARBOPOL ® ETD 2020 0.2567D Polymer Z, Ex. 1 0.5 6.5 88.9 34,400 CARBOPOL ® 980 0.5 67E PolymerZ, Ex. 1 0.75 6.4 81.8 42,000 CARBOPOL ® 980 0.5 67F Polymer Z, Ex. 1 16.4 82.7 40,200 CARBOPOL ® 980 0.25 67G Polymer Z, Ex. 1 0.5 6.5 90.551,200 CARBOPOL ® Ultrez 21 0.5 67H Polymer Z, Ex. 1 0.75 6.5 90.159,800 CARBOPOL ® Ultrez 21 0.5 67I Polymer Z, Ex. 1 1 6.5 89.3 45,900CARBOPOL ® Ultrez 21 0.25

TABLE 38 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. % pHClarity (24 hours) 68A Polymer AT, Ex. 1 0.5 6.5 87.5 56,400 CARBOPOL ®ETD 2020 0.5 68B Polymer AT, Ex. 1 0.75 6.5 85.5 83,200 CARBOPOL ® ETD2020 0.5 68C Polymer AT, Ex. 1 1 6.5 80.9 45,600 CARBOPOL ® ETD 20200.25 68D Polymer AT, Ex. 1 0.5 6.5 84.7 45,800 CARBOPOL ® 980 0.5 68EPolymer AT, Ex. 1 0.75 6.5 82.7 62,800 CARBOPOL ® 980 0.5 68F PolymerAT, Ex. 1 1 6.5 81.1 39,200 CARBOPOL ® 980 0.25 68G Polymer AT, Ex. 10.5 6.5 88.1 72,800 CARBOPOL ® Ultrez 21 0.5 68H Polymer AT, Ex. 1 0.756.5 84.6 98,200 CARBOPOL ® Ultrez 21 0.5 68I Polymer AT, Ex. 1 1 6.584.5 67,400 CARBOPOL ® Ultrez 21 0.25 68J Polymer AT, Ex. 1 0.5 6.5 77.839,400 STABYLEN ® 30 0.5 68K Polymer AT, Ex. 1 0.75 6.4 71.8 43,200STABYLEN ® 30 0.5 68L Polymer AT, Ex. 1 1 6.4 66.5 31,800 STABYLEN ® 300.25

TABLE 39 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. % pHClarity (24 hours) 69A Polymer AU, Ex. 1 0.5 6.4 88.6 57,800 CARBOPOL ®ETD 2020 0.5 69B Polymer AU, Ex. 1 0.75 6.5 89.5 73,400 CARBOPOL ® ETD2020 0.5 69C Polymer AU, Ex. 1 1 6.5 87.9 55,800 CARBOPOL ® ETD 20200.25 69D Polymer AU, Ex. 1 0.5 6.5 89.9 43,400 CARBOPOL ® 980 0.5 69EPolymer AU, Ex. 1 0.75 6.5 89.8 58,200 CARBOPOL ® 980 0.5 69F PolymerAU, Ex. 1 1 6.5 89.3 47,600 CARBOPOL ® 980 0.25 69G Polymer AU, Ex. 10.5 6.5 89.2 70,000 CARBOPOL ® Ultrez 21 0.5 69H Polymer AU, Ex. 1 0.756.5 85.8 79,800 CARBOPOL ® Ultrez 21 0.5 69I Polymer AU, Ex. 1 1 6.588.5 51,600 CARBOPOL ® Ultrez 21 0.25

A second series of aqueous gels containing each of the foregoing ASAPwas prepared following the procedure described above except that, afterthe selected commercial thickener was dispersed in water, the selectedASAP was added and the resulting combination was then neutralized withAMP (95%) to about pH 6-6.5. The % clarity and 24-hour viscosity resultsachieved for this second series of aqueous gels were substantiallysimilar to those of the corresponding ASAP-containing gels in the firstseries of aqueous gels.

The results show that the ASAP of this invention can be employed incombination with either conventional carbomer, or modified carbomer,thickeners in aqueous gel, without sacrificing viscosity.

For comparison, the viscosity achieved in an aqueous gel with theAMP-neutralized commercial polymer in the absence of ASAP is shown inTable 40.

TABLE 40 Active Viscosity mPa · s Polymer in Gel Wt. % pH (24 hours)CARBOPOL ® ETD 2020 0.5 6.3 26,500-26,600 CARBOPOL ® ETD 2020 0.25 6.316,650 CARBOPOL ® 980 0.5 6.4 43,800 CARBOPOL ® 980 0.25 6.4 27,900CARBOPOL ® Ultrez 21 0.5 6.4 46,800-46,950 CARBOPOL ® Ultrez 21 0.25 6.435,600 STABYLEN ® 30 0.5 6.5 16,100 STABYLEN ® 30 0.25 6.5 12,600

EXAMPLE 70 Aqueous Gels

This example demonstrates the use of ASAP, Polymer AT of Example 1, incombination with commercial hydrophobically-modified carbomer polymer,CARBOPOL® Ultrez 21 (Noveon, Inc., Cleveland Ohio) in beneficiallyachieving an unexpected increase in viscosity while maintaining thedesirable aesthetic and gel pick-up product properties associated withgels produced with such commercially available polymer.

Aqueous gels were prepared containing the varying amounts of eachpolymer shown in Table 41 below. The gels were prepared by adding thecommercial polymer to the water and pre-dispersing it by admixing withstirring for about 15 minutes, avoiding entraining air, and allowing theadmixture to stand without stirring for about 30 minutes to provide apolymer dispersion. The requisite amount of Polymer AT emulsion was thenadmixed into the foregoing polymer dispersion and sufficient AMP (95%)was added to the polymeric mixture to adjust the pH to a range of about6.4-6.8 to form a gel.

Two series of gels were prepared containing, on a composition weightbasis, either a total polymer content of about 1.25 active weight % (Ex.70A-F) or about 1 active weight % (Ex. 70G-K). The viscosity wasdetermined by Method A. Gel pick-up was subjectively evaluated bydipping three fingers into the gel to scoop a dollop of gel andobserving the cushioning properties of the gel adhering to the fingers.The term “cushioning” refers generally to the firmness of a gel and theability of a dollop of gel to adhere to the fingers and hold a firm peak(i.e., a peaking gel). Gel pick-up was subjectively rated on the basisof observed cushioning as follows: excellent=pronounced and sustainedpeak, very good=medium and sustained peak, good=slight to medium peak,marginal=slight peak, and weak=no peak, smooth. Gel pick-up is a sensoryproduct attribute that a consumer observes when the user physicallyremoves gel from a container, such as a jar, or squeezes a gel out of atube onto the fingers for application to the skin or hair. The resultsof the viscosity and gel pick-up evaluations are shown in Table 41.

TABLE 41 Weight % Weight % Brookfield Example Polymer AT, CARBOPOL ®Viscosity No. (Ex. 1) Ultrez 21 (mPa · s) Gel Pick-Up 70A 1.25 — 21,200Weak 70B 1 0.25 60,400 Good 70C 0.75 0.5 97,600 Very Good 70D 0.5 0.75125,000 Excellent 70E 0.25 1 125,000 Excellent 70F — 1.25 93,600Excellent 70G 1 — 11,400 Marginal 70H 0.75 0.25 21,800 Good 70I 0.5 0.567,200 Very Good 70J 0.25 0.75 93,800 Excellent 70K — 1 76,600 Excellent

The results show an unexpected increase in viscosity was achieved at atotal polymer content of about 1.25 active weight % when the weightratio of ASAP:commercial polymer was about 3:2 (Ex. 70C), about 2:3 (Ex.70D) and about 1:4 (Ex. 70E). At a total polymer content of about 1active weight %, an unexpected increase in viscosity was achieved whenthe weight ratio of ASAP:commercial polymer was about 1:3 (Ex. 70J).

The gel pick-up of Exs. 70B-E and Exs. 70H-J was judged good toexcellent, indicating the compatibility of ASAP with the commercialpolymer.

It was surprisingly found that alkali-swellable ASAP can be used incombination with anionic polymeric thickener, such as carbomer polymeror hydrophobically modified carbomer polymer, to provide a viscositythat is unexpectedly higher than the sum of the viscosity of theindividual polymers at the same concentration.

From the foregoing examples, it can be seen that the present inventivepolymers can be used in a wide variety of different aqueous andhydro-alcoholic compositions. The foregoing discussion and reportedstudies are intended to be illustrative of the present invention and arenot to be taken as limiting. Still other variants within the spirit andscope of this invention are possible and will readily present themselvesto those skilled in the art.

1. A composition comprising an associative polymer and water having a pHof greater than about 2 wherein said polymer is the product ofpolymerization of a monomer mixture comprising: (a) at least one acidicvinyl monomer or a salt thereof; (b) at least one nonionic vinylmonomer; (c) a first associative monomer having a first hydrophobic endgroup; (d) at least one monomer selected from a second associativemonomer having a second hydrophobic end group, a semihydrophobicmonomer, and a combination thereof; and, optionally, (e) a monomerselected from a crosslinking monomer, a chain transfer agent, or acombination thereof; with the proviso that when monomer (d) is a secondassociative monomer and said semihydrophobic monomer is not present, thefirst and second hydrophobic end groups of associative monomers (c) and(d) are each selected from a substituted or unsubstituted C₂₂ and C₁₂linear alkyl, respectively; wherein said first and second associativemonomers are selected from at least one monomer of the formula:

wherein, each R² is independently H, methyl, —C(O)OH, or —C(O)OR³; R³ isC₁-C₃₀ alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—,—C(O)NH—, —Ar—(CE₂)_(z)—NHC(O)O—, —Ar—(CE₂)_(z)—NHC(O)NH—, or—CH₂CH₂NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; kis an integer in the range of 0 to about 30, and m is 0 or 1, with theproviso that when k is 0, m is 0, and when k is in the range of 1 toabout 30, m is 1; (R⁴—O)_(n) is a polyoxyalkylene, which is ahomopolymer, a random copolymer, or a block copolymer of C₂-C₄oxyalkylene units, wherein R⁴ is C₂H₄, C₃H₆, C₄H₈, and n is an integerin the range of about 5 to about 250, Y is —R⁴O—, —R⁴NH—, —C(O)—,—C(O)NH—, —R⁴NHC(O)NH—, or —C(O)NHC(O)—; and R⁵ is a substituted orunsubstituted alkyl selected from a C₈-C₄₀ linear alkyl, a C₈-C₄₀branched alkyl, a C₈-C₄₀ carbocyclic alkyl, a C₂-C₄₀ alkyl-substitutedphenyl, an aryl-substituted C₂-C₄₀ alkyl, or a C₈-C₈₀ complex ester;wherein the R⁵ alkyl group optionally comprises one or more substituentsselected from a hydroxyl group, an alkoxyl group, or a halogen group;and said semihydrophobic monomer is selected from at least one monomerof the formulas:

wherein, in each of formulas (IV) and (V), each R⁶ is independently H,C₁-C₃₀ alkyl, —C(O)OH, or —C(O)OR⁷; R⁷ is C₁-C₃₀ alkyl; A is —CH₂C(O)O—,—C(O)O—, —O—, —CH₂O—, —NHC(O)NH—, —C(O)NH—, —Ar—(CE₂)_(z)—NHC(O)O—,—Ar—(CE₂)_(z)—NHC(O)NH—, or —CH₂CH₂NHC(O)—; Ar is a divalent aryl; E isH or methyl: z is 0 or 1; p is an integer in the range of 0 to about 30,and r is 0 or 1, with the proviso that when p is 0, r is 0, and when pis in the range of 1 to about 30, r is 1; (R⁸—O)_(v) is apolyoxyalkylene, which is a homopolymer, a random copolymer or a blockcopolymer of C₂-C₄ oxyalkylene units, wherein R⁸ is C₂H₄, C₃H₆ or C₄H₈,and v is an integer in the range of about 5 to about 250, R⁹ is H orC₁-C₄ alkyl; and D is a C₈-C₃₀ unsaturated alkyl or acarboxy-substituted C₈-C₃₀ unsaturated alkyl.
 2. The composition ofclaim 1 further comprising a pH adjusting agent, a buffering agent, afixative, a film former, an auxiliary rheology modifier, a hairconditioning agent, a skin conditioning agent, a chemical hair waving orstraightening agent, a colorant, a surfactant, a polymer film modifyingagent, a product finishing agent, a propellant, or a mixture thereof. 3.The composition of claim 1 further comprising a carbomer polymer or ahydrophobically-modified carbomer polymer.
 4. The composition of claim 1further comprising a silicone polymer.
 5. The composition of claim 1further comprising a C₁-C₈ monohydric alcohol, a C₁-C₈ polyol or mixturethereof.
 6. The composition of claim 1 wherein the composition is in theform of a liquid, a gel, a spray, an emulsion, a semisolid, or a solid.7. The composition of claim 1 further comprising emulsifiers, emulsionstabilizers, waxes, dispersants, and viscosity control agents, solvents,electrolytes, synthetic oils, vegetable oils animal oils, silicone oils,monomeric or polymeric quaternized ammonium salts, emollients,humectants, lubricants, sunscreen agents, hair colorants, pigments,dyes, surfactants, polymer film modifying agents, humectants,tackifiers, detackifiers, wetting agents, chelating agents, opacifiers,pearlescing agents, preservatives, fragrances, solubilizers, UVabsorbers, propellants, compressed gases, or mixtures thereof.
 8. Thecomposition of claim 2 wherein said surfactant is selected from anionic,cationic, nonionic, amphoteric or zwitterionic surfactants.
 9. Thecomposition of claim 7 wherein said surfactant is selected from anionic,cationic, nonionic, amphoteric or zwitterionic surfactants.
 10. Thecomposition of claim 1 wherein the acidic vinyl monomer is selected froma carboxylic acid-containing vinyl monomer, a sulfonic acid-containingvinyl monomer, a phosphonic acid-containing vinyl monomer, or acombination thereof.
 11. The composition of claim 1 wherein the acidicvinyl monomer is acrylic acid, methacrylic acid, styrenesulfonic acid,2-acrylamido-2-methylpropane sulfonic acid, or a combination thereof.12. The composition of claim 1 wherein the salt is selected from analkali metal salt, an alkaline earth metal salt, an ammonium salt, analkyl-substituted ammonium salt, or a combination thereof.
 13. Thecomposition of claim 1 wherein the nonionic vinyl monomer is a compoundselected from at least one of the following formulas:CH₂═C(X)Z  (I)CH₂═CH—OC(O)R  (II) wherein, in each of formulas (I) and (II), X is H ormethyl; Z is BC(O)OR¹, —C(O)NH₂, —C(O)NHR¹, —C(O)N(R¹)₂, —C₆H₄R¹,—C₆H₄OR¹, —C₆H₄Cl, —CN, —NHC(O)CH₃, —NHC(O)H, N-(2-pyrrolidonyl),N-caprolactamyl, —C(O)NHC(CH₃)₃, —C(O)NHCH₂CH₂—N-ethyleneurea, —SiR₃,—C(O)O(CH₂)_(x)SiR₃, —C(O)NH(CH₂)_(x)SiR₃, or —(CH₂)_(x)SiR₃; x is aninteger in the range of 1 to about 6; each R is independently C₁-C₁₈alkyl; each R¹ is independently C₁-C₃₀ alkyl, hydroxy-substituted C₁-C₃₀alkyl, or halogen-substituted C₁-C₃₀ alkyl.
 14. The composition of claim1 wherein the nonionic vinyl monomer is selected from a C₁-C₈ ester ofacrylic acid, a C₁-C₈ ester of methacrylic acid, or a combinationthereof.
 15. The composition of claim 1 wherein the first and secondassociative monomers each comprise a polymerizable, unsaturated endgroup, a C₈-C₄₀ alkyl hydrophobic end group, and a polyoxyalkylene groupdisposed between and covalently bonded to the unsaturated end group andthe hydrophobic end group.
 16. The composition of claim 15 wherein thepolyoxyalkylene group is a homopolymer, a random copolymer, or a blockcopolymer comprising about 5 to about 250 C₂-C₄ oxyalkylene units. 17.The composition of claim 1 wherein the monomer mixture includes at leastone semihydrophobic monomer having a polymerizable, unsaturated endgroup and a polyoxyalkylene group covalently bonded thereto.
 18. Thecomposition of claim 17 wherein the polyoxyalkylene group is ahomopolymer, a random copolymer, or a block copolymer comprising about 5to about 250 C₂-C₄ oxyalkylene units.
 19. The composition of claim 1wherein the monomer mixture includes a semihydrophobic monomer havingone of the following chemical formulas:CH₂═CH—O—(CH₂)_(a)—O—(C₃H₆O)_(b)—(C₂H₄O)_(c)—H orCH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(e)—H; wherein a is 2, 3, or 4; b is aninteger in the range of 1 to about 10; c is an integer in the range ofabout 5 to about 50; d is an integer in the range of 1 to about 10; ande is an integer in the range of about 5 to about
 50. 20. The compositionof claim 1 wherein the monomer mixture contains at least one crosslinking monomer.
 21. The composition of claim 20 wherein thecrosslinking monomer is an acrylate ester of a polyol having at leasttwo acrylate ester groups, a methacrylate ester of a polyol having atleast two methacrylate ester groups or a combination thereof.
 22. Thecomposition of claim 1 wherein the monomer mixture contains at least onechain transfer agent.
 23. The composition of claim 22 wherein the chaintransfer agent is selected from a thio compound, a disulfide compound, aphosphite, a hypophosphite, a haloalkyl compound, or a combinationthereof.